CN113351184B - Nylon ferroferric oxide adsorbing material containing carboxyl and preparation method thereof - Google Patents

Nylon ferroferric oxide adsorbing material containing carboxyl and preparation method thereof Download PDF

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CN113351184B
CN113351184B CN202110667895.4A CN202110667895A CN113351184B CN 113351184 B CN113351184 B CN 113351184B CN 202110667895 A CN202110667895 A CN 202110667895A CN 113351184 B CN113351184 B CN 113351184B
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nylon
nano particles
carboxyl
ferroferric oxide
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CN113351184A (en
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侯成敏
钱志云
严薇
刘甜
杨佳琦
张�杰
张兴
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Xian University of Technology
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Abstract

The invention discloses a preparation method of a carboxyl-containing nylon ferroferric oxide adsorbing material, which is implemented according to the following steps: step one, fe 3 O 4 Preparation of magnetic micro-nano particles and Fe 3 O 4 Amino functionalization of the magnetic micro-nano particles; step two, pretreating the nylon base material, and adding the pretreated nylon base material, acrylic monomers, an initiator and an acetone aqueous solution into a flask to prepare a nylon base material; step three, carrying out amination on Fe obtained in the step one 3 O 4 And (3) carrying out composite reaction on the micro-nano particles, the nylon substrate material obtained in the step two and polyacrylic acid for 1-24 hours at normal temperature to obtain the carboxyl-containing nylon ferroferric oxide adsorbing material. The invention discloses a carboxyl-containing nylon ferroferric oxide adsorbing material which can relieve pure Fe 3 O 4 The magnetic micro-nano adsorbing material has the defects of heavy mass and high sinking speed in a water body, so that the adsorption efficiency is low.

Description

Nylon ferroferric oxide adsorbing material containing carboxyl and preparation method thereof
Technical Field
The invention belongs to the technical field of polymer materials, and particularly relates to a nylon ferroferric oxide adsorbing material containing carboxyl, and a preparation method of the nylon ferroferric oxide adsorbing material containing carboxyl.
Background
With the rapid development of the industry in China, the wastewater containing heavy metal ions not only poses great threat to the ecological system, but also has great harm to the human health. Thus, in greenUnder the mainstream trend of color sustainable development, solving the pollution problem of heavy metal ion wastewater becomes urgent. Most of the existing methods for treating heavy metal ions are electrochemical methods, precipitation methods, biological flocculation methods, ion exchange methods, membrane separation methods, adsorption methods and the like, and the methods have the defects of high cost, difficult recovery of an adsorbent and secondary pollution. Micro-nano ferroferric oxide (Fe) 3 O 4 ) The material has good magnetic property, simple preparation process, low price, low toxicity, easy magnetic separation and recovery, and micro-nano Fe 3 O 4 The material has extremely high specific surface area, so that the material has high surface activity and is easy to modify functional groups, and the adsorbent material is favorable for showing good adsorption performance.
CN106315739A discloses a method for adsorbing chromium ions by using functionalized magnetic ferroferric oxide, which is mainly technically characterized in that: firstly, magnetic ferroferric oxide is synthesized and functionalized by cetyl trimethyl ammonium bromide and 2-thenoyl trifluoroacetone to obtain the functionalized magnetic ferroferric oxide, under a certain condition, the maximum adsorption capacity of the functionalized magnetic ferroferric oxide to chromium ions is 1000mg/g or even higher, the adsorbed functionalized magnetic ferroferric oxide can be desorbed by hydrochloric acid (HCl) with a certain concentration, and the desorption rate reaches 95.88%. The maximum adsorption capacity of the secondary adsorption of the regenerative functionalized magnetic ferroferric oxide is 957.8mg/g.
CN111229170A discloses an amino acid modified cellulose composite ferric oxide adsorbent, a preparation method and an application thereof, and the main technical characteristics are that: firstly, adding microcrystalline cellulose into a sodium hydroxide-urea-thiourea mixed solution, uniformly stirring, and freezing at-10 ℃. After thawing, adding an amino acid modified solution, stirring at a certain temperature, fully reacting to obtain an amino acid modified cellulose solution, adding a proper amount of tween 80, sodium dodecyl sulfate and ferroferric oxide powder, fully stirring at 50-70 ℃, washing, filtering and drying a product by deionized water to obtain the amino acid modified cellulose composite ferroferric oxide adsorbent. The amino acid modified cellulose composite ferric oxide adsorbent for removing lead ions has the characteristics of high adsorption efficiency, low cost, reusability and environmental protection, and has wide application prospect in removing lead pollution in wastewater.
Nylon, a polyamide polymer also known as chinlon, is the most widely used synthetic fiber, has the characteristics of no toxicity, light weight, high mechanical strength, good wear resistance, corrosion resistance, swelling resistance, multiple varieties, large yield and the like, and is widely applied to the industrial and domestic fields.
At present, the adsorption material for treating heavy metal wastewater commonly used comprises polysaccharide substances (starch and cellulose) and modified substances thereof, the related research on the preparation of the material for adsorbing heavy metal ions by taking nylon as a base material is less, the weight of the nylon base material is lighter, and the pure Fe can be relieved 3 O 4 The magnetic micro-nano adsorbing material has the defects of heavy mass and high sinking speed in a water body, so that the adsorption efficiency is low.
Disclosure of Invention
The invention aims to provide a carboxyl-containing nylon ferroferric oxide adsorbing material which can relieve pure Fe 3 O 4 The magnetic micro-nano adsorption material has the defects of heavy mass and high sinking speed in a water body, so that the adsorption efficiency is low.
The second purpose of the invention is to provide a preparation method of a carboxyl-containing nylon ferroferric oxide adsorbing material.
The technical scheme adopted by the invention is that the preparation method of the carboxyl-containing nylon ferroferric oxide adsorbing material is implemented according to the following steps:
step one, fe 3 O 4 Preparation of magnetic micro-nano particles and Fe 3 O 4 Amino functionalization of the magnetic micro-nano particles;
step two, pretreating the nylon base material, and adding the pretreated nylon base material, acrylic monomers, an initiator and an acetone aqueous solution into a flask to prepare a nylon base material;
step three, carrying out amination on Fe obtained in the step one 3 O 4 Carrying out composite reaction on the micro-nano particles, the nylon substrate material obtained in the step two and polyacrylic acid for 1-24 hours at normal temperature to obtain carboxyl-containing nylon ferroferric oxideAdsorbing the material.
The present invention is also characterized in that,
in step one, fe 3 O 4 The preparation method of the magnetic micro-nano particles is a coprecipitation method, and comprises the following specific steps: feCl 3 ·6H 2 O、FeSO 4 ·7H 2 O, naOH and water are added into a flask in sequence, a mechanical stirrer and a thermometer are arranged, and the mixture is continuously stirred and reacted for 2 to 12 hours at the temperature of 60 to 130 ℃ and the rotating speed of 100 to 1000rpm to generate Fe 3 O 4 Magnetic micro-nano particles, feSO 4 ·7H 2 O、FeCl 3 ·6H 2 O, naOH and water in a mass ratio of 1:1 to 6:0.5 to 5:15 to 30 percent;
in step one, fe 3 O 4 The amino functionalization of the magnetic micro-nano particles specifically comprises the following steps:
the prepared Fe 3 O 4 Dissolving the magnetic micro-nano particles and KH550 in 75% ethanol aqueous solution, adding triethylamine to adjust the pH value to 9, and carrying out condensation reflux at 80-110 ℃ for 6-10 h to obtain aminated Fe 3 O 4 Micro-nano particles; wherein, fe 3 O 4 The mass ratio of the magnetic micro-nano particles to the KH550 is 1:0.5 to 10.
In the second step, firstly, 0.2 to 0.6 weight percent of sodium carbonate solution is used for heating for 0.5 to 6 hours at the constant temperature of 60 ℃, and then 0.5 to 1.5mol/L of HCl is used for heating for 2 to 7 hours at the constant temperature of 55 ℃ in a constant-temperature water bath kettle to pre-treat the nylon base material; the nylon base material is PA6, PA66, PA11, PA12, PA1010, PA610 or PA612;
in the second step, the nylon base material after pretreatment, the acrylic monomer, the initiator and the acetone aqueous solution with the volume concentration of 40-50% are continuously stirred and reacted for 1-24 h at the rotating speed of 100-1000 rpm under the conditions of vacuum and 45-80 ℃ to obtain the nylon base material, wherein the mass ratio of the nylon base material after pretreatment, the acrylic monomer, the initiator and the acetone aqueous solution with the volume concentration of 40-50% is 4-10: 5 to 80:1:150 to 300.
In the second step, the acrylic monomer comprises one or a combination of two or more of glycidyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, hydroxyethyl acrylate and hydroxypropyl acrylate.
In the second step, the initiator is benzoyl peroxide or azobisisobutyronitrile, and the mass ratio of the acrylic monomer to the initiator is 5-80: 1;
in the third step, nylon base material and aminated Fe 3 O 4 The mass ratio of the micro-nano particles to the polyacrylic acid is 5-80: 1:0.5 to 8.
The second technical scheme adopted by the invention is that the carboxyl-containing nylon ferroferric oxide adsorbing material is prepared by the preparation method.
The invention has the beneficial effects that:
(1) The method has simple preparation process, uses reagents which are common medicines available on the market, has low cost, strong operability and economic benefit, and can be used for large-scale production;
(2) Due to Fe 3 O 4 The magnetic iron-based composite material has good magnetism and extremely high specific surface area, the prepared adsorbing material is easy to recover, and simultaneously Fe is added 3 O 4 The acting force between the substrate and the substrate material reduces the possibility of secondary pollution to the environment;
(3) The adsorbing material prepared by the invention takes nylon as a base material, so that the defect of pure Fe is overcome 3 O 4 The magnetic micro-nano adsorption material has the defects of heavy mass and high sinking speed in a water body, so that the adsorption efficiency is low, and the nylon material is modified by using the acrylic monomer to enhance the nylon and the Fe 3 O 4 The acting force among the magnetic micro-nano particles can be recycled; the polyacrylic acid can enhance the adsorption capacity of the adsorption material on heavy metal ions, has good adsorption effect on the heavy metal ions such as copper ions, chromium ions, lead ions, cadmium ions and the like, has the adsorption rate of up to 90 percent on the copper ions, is recycled for 14 times, has the adsorption rate of more than 80 percent at most, and can be widely applied to the fields of wastewater treatment such as electroplating wastewater, metal mine exploitation, smelting and the like.
(4) The adsorption material prepared by the invention has good adsorption stability, and can be applied to the fields of electroplating wastewater treatment, metal mining and smelting wastewater treatment, domestic wastewater treatment and the like.
Drawings
FIG. 1 is a graph of the number of cycles of use of the adsorbent material of example 1 versus regenerable efficiency;
FIG. 2 is a graph showing the relationship between the adsorption time, the adsorption capacity and the total amount of adsorption of the adsorbent in example 1.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention provides a preparation method of a carboxyl-containing nylon ferroferric oxide adsorbing material, which is implemented according to the following steps:
step one, fe 3 O 4 Preparation of magnetic micro-nano particles and Fe 3 O 4 Amino functionalization of the magnetic micro-nano particles;
in step one, fe 3 O 4 The preparation method of the magnetic micro-nano particles is a coprecipitation method, and comprises the following specific steps: feCl 3 ·6H 2 O、FeSO 4 ·7H 2 O, naOH and water are added into a flask in sequence, a mechanical stirrer and a thermometer are arranged, and the mixture is continuously stirred and reacted for 2 to 12 hours at the temperature of between 60 and 130 ℃ at the rotating speed of between 100 and 1000rpm to generate Fe 3 O 4 Magnetic micro-nano particles, feSO 4 ·7H 2 O、FeCl 3 ·6H 2 O, naOH and water in a mass ratio of 1:1 to 6:0.5 to 5:15 to 30 percent;
in step one, fe 3 O 4 The amino functionalization of the magnetic micro-nano particles specifically comprises the following steps:
the prepared Fe 3 O 4 Dissolving the magnetic micro-nano particles and KH550 in 75% ethanol aqueous solution, adding triethylamine to adjust the pH value to 9, and carrying out condensation reflux at 80-110 ℃ for 6-10 h to obtain aminated Fe 3 O 4 Micro-nano particles; wherein, fe 3 O 4 The mass ratio of the magnetic micro-nano particles to the KH550 is 1:0.5 to 10.
The amino functional substance comprises KH550, triethylene tetramine, ethylenediamine, amino acid, isopropylamine, aromatic amine, butanediamine, pentanediamine, putrescine, cadaverine, spermine, diaminobenzidine and the like.
Step two, pretreating the nylon base material, and adding the pretreated nylon base material, acrylic monomers, an initiator and an acetone aqueous solution into a flask to prepare a nylon base material;
in the second step, firstly, 0.2 to 0.6 weight percent of sodium carbonate solution is used for heating for 0.5 to 6 hours at the constant temperature of 60 ℃, and then 0.5 to 1.5mol/L of HCl is used for heating for 2 to 7 hours at the constant temperature of 55 ℃ in a constant-temperature water bath kettle to pre-treat the nylon base material; the nylon base material is PA6, PA66, PA11, PA12, PA1010, PA610 or PA612; the mass ratio of the sodium carbonate aqueous solution to the HCl to the nylon base material is 80-180: 300 to 750:1.
in the second step, the pretreated nylon base material, the acrylic monomer, the initiator and the acetone aqueous solution with the volume concentration of 40-50% are continuously stirred and reacted for 1-24 h at the rotating speed of 100-1000 rpm under the conditions of vacuum and 45-80 ℃ to obtain the nylon base material, wherein the mass ratio of the pretreated nylon base material, the acrylic monomer, the initiator and the acetone aqueous solution with the volume concentration of 40-50% is 4-10: 5 to 80:1:150 to 300.
In the second step, the acrylic monomer comprises one or a combination of two or more of glycidyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, hydroxyethyl acrylate and hydroxypropyl acrylate.
In the second step, the initiator is benzoyl peroxide or azobisisobutyronitrile, and the mass ratio of the acrylic monomer to the initiator is 5-80: 1;
step three, carrying out amination on Fe obtained in the step one 3 O 4 And (3) carrying out composite reaction on the micro-nano particles, the nylon substrate material obtained in the step two and polyacrylic acid for 1-24 hours at normal temperature to obtain the carboxyl-containing nylon ferroferric oxide adsorbing material.
In the third step, nylon base material and aminated Fe 3 O 4 Micro-nano particles and polypropyleneThe mass ratio of the olefine acid is 5-80: 1:0.5 to 8.
The invention also provides a nylon ferroferric oxide adsorbing material containing carboxyl, which is prepared by the preparation method.
Drying and grinding the nylon ferroferric oxide adsorbing material containing carboxyl into powder, adding 1-50 mg of adsorbing material into waste liquid with the pH value of 1-12 and the concentration of 1-100 mg/L at normal temperature, and adsorbing for 1-5 h; the waste liquid is any one or combination of two or more of copper ions, chromium ions, lead ions and cadmium ions, the adsorption efficiency is 10-99%, the unit adsorption amount is 2-80 mg/g, and the regenerable efficiency is 50-99%.
And D, carrying out heavy metal ion adsorption performance test on the carboxyl-containing nylon ferroferric oxide adsorption material obtained in the step three, wherein the test method comprises the following steps: preparing a heavy metal ion solution with the concentration of 1-100 mg/L, putting 10mL into a 20mL small glass bottle, adjusting the pH value to 1-12, adding 1-50 mg of a carboxyl-containing nylon ferroferric oxide adsorbing material, stirring for 1 min-5 h, carrying out magnetic separation for 5min, and taking supernate and measuring the concentration of the metal ion solution by using an atomic spectrophotometer.
And D, carrying out a renewable effect test on the carboxyl-containing nylon ferroferric oxide adsorbing material obtained in the step three, wherein the method comprises the following steps:
(1) Preparing a metal ion solution, putting 10mL of the metal ion solution into a 20mL glass bottle, adding a nylon-based magnetic adsorbent material, stirring for 3 hours at room temperature, separating by a magnet for 5min, removing a supernatant, and calculating unit adsorption amount and removal rate;
unit adsorption amount:
Figure GDA0003718169810000081
the removal rate is as follows:
Figure GDA0003718169810000082
wherein:
C 0 : initial concentration of heavy metal ions, unit mg/L;
C v : the equilibrium concentration of heavy metal ions is unit mg/L;
v: adsorption solution volume, unit L;
m: mass of adsorbent material, in g.
(2) 0.1mol/L disodium ethylene diamine tetraacetate (Na) is used 2 EDTA) 20mL of solution, stirring for 6h, performing magnetic separation for 5min, and removing the supernatant;
(3) Centrifugally washing the desorbed adsorbing material for three times by using a centrifugal machine at 10000r/min, and drying;
the steps (1) to (3) are 1 cycle, 14 cycles are carried out in total, and the renewable effect of the carboxyl-containing nylon ferroferric oxide adsorption material is calculated according to the following formula:
Figure GDA0003718169810000083
wherein:
Q i : the unit adsorption amount of the adsorption material in the ith cycle test;
Q 1 : unit adsorption amount of adsorbent material at 1 st cycle test.
Example 1
(1) Respectively adding 12g of FeCl 3 ·6H 2 O、6g FeSO 4 ·7H 2 O, 7g NaOH and 150mL water are sequentially added into a flask, a mechanical stirrer and a thermometer are arranged, and the reaction is continuously stirred at the rotating speed of 300rpm for 3 hours at the temperature of 90 ℃ to generate Fe 3 O 4 Magnetic nanoparticles. Then, 1g of Fe 3 O 4 Dissolving magnetic micro-nano particles and 2g KH550 in 50mL of 75% ethanol aqueous solution, adding 4mL of triethylamine to adjust the pH value to 9, and carrying out condensation reflux at 90 ℃ for 6h to obtain aminated Fe 3 O 4 Micro-nano particles.
(2) PA6 was pretreated first with 50mL0.4wt% sodium carbonate solution at 60 ℃ for 3h and then with 220mL of 1mol/L HCl in a water bath at 55 ℃ for 3 h. 0.3g of pretreated PA6, 0.68g of glycidyl methacrylate, 0.62g of hydroxyethyl methacrylate, 15mL of a 46% acetone aqueous solution by volume and 90mg of benzoyl peroxide are added into a flask, and the mixture is continuously stirred and reacted at 60 ℃ for 24 hours at the rotating speed of 500rpm under vacuum to generate the nylon base material.
(3) 0.5g of the aminated Fe obtained in (1) 3 O 4 And (3) reacting the micro-nano particles, 6g of the nylon substrate material obtained in the step (2) and 1.5g of polyacrylic acid at normal temperature for 3 hours to obtain the carboxyl-containing nylon ferroferric oxide adsorbing material.
(4) And (3) carrying out copper ion adsorption performance test on the magnetic nylon adsorption material containing carboxyl: preparing 8.33mg/L copper ion solution, putting 10mL into a small glass bottle, adjusting the pH value to 9, adjusting the temperature to 25 ℃, adding 37.5mg of adsorbing material, stirring for 2 hours, separating by a magnet for 5min as shown in figure 2, measuring the unit adsorption capacity to be 2.284mg/g, the removal rate to be 87.5 percent as shown in figure 1, and the regenerable effect to be 86.84 percent after 14 cycles.
Example 2
(1) 21g of FeCl 3 ·6H 2 O、7g FeSO 4 ·7H 2 O, 14g NaOH and 150mL water are sequentially added into a flask, a mechanical stirrer and a thermometer are arranged, and the mixture is continuously stirred and reacted for 4 hours at the rotating speed of 600rpm at 70 ℃ to generate Fe 3 O 4 Magnetic nanoparticles. Then, 1g of Fe 3 O 4 Dissolving magnetic micro-nano particles and 1g KH550 in 50mL of 75% ethanol aqueous solution, adding 4mL of triethylamine to adjust the pH value to 9, and carrying out condensation reflux at 80 ℃ for 7h to obtain aminated Fe 3 O 4 Micro-nano particles.
(2) PA66 was pretreated first with 50mL0.2wt% sodium carbonate solution at 60 ℃ for 6h and then with 220mL0.5mol/L HCl in a water bath at 55 ℃ for 7 h. 0.32g of pretreated PA66, 0.6g of glycidyl methacrylate, 0.7g of methyl methacrylate, 16mL of 40 vol% aqueous acetone solution and 100mg of benzoyl peroxide were added to the flask, and the mixture was reacted under vacuum at 70 ℃ for 20 hours with continuous stirring at 600rpm to give a nylon base material.
(3) 0.25g of the aminated Fe obtained in (1) 3 O 4 The micro-nano particles, 6g of the nylon substrate material obtained in the step (2) and 1.5g of polyacrylic acid react for 5 hours at normal temperature to prepare the carboxyl-containing nylon tetraoxideAn iron adsorbent material.
(4) A magnetic nylon adsorbing material containing carboxyl is subjected to a lead ion adsorption performance test: preparing 20mg/L lead ion solution, putting 10mL into a small glass bottle, adjusting the pH value to 9, adjusting the temperature to 25 ℃, adding 20mg of adsorbing material, stirring for 5 hours, separating by a magnet for 5 minutes, measuring the unit adsorbing amount of 5.265mg/g, the removal rate of 81.34 percent and the reproducible effect of 76.43 percent after 14 cycles.
Example 3
(1) Respectively adding 15g of FeCl 3 ·6H 2 O、5g FeSO 4 ·7H 2 O, 15g NaOH and 150mL water were added in sequence to a flask equipped with a mechanical stirrer and a thermometer, and the reaction was continuously stirred at 100 ℃ at 700rpm for 5 hours to produce Fe 3 O 4 Magnetic nanoparticles. Then, 2g of Fe 3 O 4 Dissolving magnetic micro-nano particles and 5g KH550 in 50mL of 75% ethanol aqueous solution, adding 4mL of triethylamine to adjust the pH value to 9, and carrying out condensation reflux at 100 ℃ for 8h to obtain aminated Fe 3 O 4 Micro-nano particles.
(2) PA11 was pretreated first with a solution of 50mL0.3wt% sodium carbonate at 60 ℃ for 4h and then with 220mL1.5mol/L HCl in a water bath at 55 ℃ for 2 h. 0.34g of pretreated PA11, 0.71g of glycidyl methacrylate, 0.56g of ethyl methacrylate, 17mL of 44 vol% aqueous acetone solution, and 60mg of benzoyl peroxide were added to the flask, and the mixture was reacted under vacuum at 65 ℃ with continuous stirring at 700rpm for 15 hours to produce a nylon base material.
(3) 0.1g of the aminated Fe obtained in (1) 3 O 4 And (3) reacting the micro-nano particles, 6g of the nylon base material obtained in the step (2) and 0.8g of polyacrylic acid at normal temperature for 8 hours to obtain the carboxyl-containing nylon ferroferric oxide adsorbing material.
(4) Carrying out chromium ion adsorption performance test on the magnetic nylon adsorption material containing carboxyl: preparing 83.3mg/L chromium ion solution, putting 10mL into a small glass bottle, adjusting the pH value to 9, adjusting the temperature to 25 ℃, adding 3.75mg of adsorbing material, stirring for 3 hours, separating by a magnet for 5min, measuring the unit adsorption quantity of 70.864mg/g, the removal rate is 71.89%, and the regenerable effect after 14 cycles is 76.79%.
Example 4
(1) Separately, 32g of FeCl 3 ·6H 2 O、8g FeSO 4 ·7H 2 O, 30g NaOH and 150mL water are sequentially added into a flask, a mechanical stirrer and a thermometer are arranged, and the reaction is continuously stirred at the rotating speed of 800rpm at the temperature of 110 ℃ for 6 hours to generate Fe 3 O 4 Magnetic nanoparticles. Then, 2g of Fe 3 O 4 Dissolving the magnetic micro-nano particles and 6g KH550 in 50mL of 75% ethanol aqueous solution, adding 4mL of triethylamine to adjust the pH value to 9, and carrying out condensation reflux at 110 ℃ for 8h to obtain aminated Fe 3 O 4 Micro-nano particles.
(2) PA6 was pretreated first by heating with 50mL0.4wt% sodium carbonate solution at 60 ℃ for 3h and then with 220mL0.6mol/L HCl in a thermostatted water bath at 55 ℃ for 6 h. 0.34g of pretreated PA6, 0.66g of glycidyl methacrylate, 0.6g of styrene, 15mL of 48 vol% aqueous acetone solution and 50mg of benzoyl peroxide are added into a flask, and the mixture is continuously stirred and reacted at 75 ℃ for 12 hours at 800rpm under vacuum to form the nylon base material.
(3) 0.15g of the aminated Fe obtained in (1) 3 O 4 And (3) reacting the micro-nano particles, 6g of the nylon base material obtained in the step (2) and 0.3g of polyacrylic acid at room temperature for 14 hours to obtain the carboxyl-containing nylon ferroferric oxide adsorbing material.
(4) And (3) carrying out copper ion adsorption performance test on the magnetic nylon adsorbing material containing carboxyl: preparing 5.6mg/L cadmium ion solution, putting 10mL cadmium ion solution in a small glass bottle, adjusting the pH value to 9, adjusting the temperature to 25 ℃, adding 5mg adsorbing material, stirring for 2 hours, separating for 5min by a magnet, measuring the unit adsorbing amount of 50.071mg/g, the removal rate of 89.84 percent, and the regenerable effect after 14 cycles is 82.01 percent.
Example 5
(1) Respectively adding 45g of FeCl 3 ·6H 2 O、9g FeSO 4 ·7H 2 O, 35g NaOH and 150mL water are sequentially added into a flask, a mechanical stirrer and a thermometer are arranged, and the reaction is continuously stirred at the rotating speed of 900rpm at the temperature of 120 ℃ for 7 hours to generate Fe 3 O 4 Magnetic nanoparticles. Then, 1g of Fe 3 O 4 Magnetic micro-nano particles and 4g KH550 is dissolved in 50mL ethanol water solution with the mass fraction of 75 percent, 4mL triethylamine is added to adjust the pH value to 9, and the mixture is condensed and refluxed for 9h at the temperature of 100 ℃ to obtain the aminated Fe 3 O 4 Micro-nano particles.
(2) PA1010 was pretreated by first heating a 50mL0.5wt% sodium carbonate solution at 60 ℃ for 2h and then at 55 ℃ for 5h in a water bath using 220mL0.8mol/L HCl. 0.4g of pretreated PA1010, 0.4g of glycidyl methacrylate, 0.6g of hydroxyethyl acrylate, 15mL of 47 vol% aqueous acetone solution and 100mg of benzoyl peroxide are added into a flask, and the mixture is continuously stirred and reacted at 80 ℃ for 10 hours at 900rpm under vacuum to form the nylon base material.
(3) 0.2g of the aminated Fe obtained in (1) 3 O 4 And (3) reacting the micro-nano particles, 6g of the nylon substrate material obtained in the step (2) and 0.1g of polyacrylic acid at normal temperature for 24 hours to obtain the carboxyl-containing nylon ferroferric oxide adsorbing material.
(4) And (3) carrying out copper ion adsorption performance test on the magnetic nylon adsorption material containing carboxyl: preparing 8.33mg/L copper ion solution, putting 10mL into a small glass bottle, adjusting the pH value to 9, adjusting the temperature to 25 ℃, adding 40mg of adsorbing material, stirring for 4 hours, separating for 5 minutes by using a magnet, measuring the unit adsorption capacity to be 2.234mg/g, wherein the removal rate is 80.05%, and the regeneration effect after 14 cycles is 75.65%.
Example 6
(1) Respectively adding 30g of FeCl 3 ·6H 2 O、10g FeSO 4 ·7H 2 O, 40g NaOH and 150mL water were added in sequence to a flask equipped with a mechanical stirrer and a thermometer, and the reaction was continuously stirred at 100 ℃ and 1000rpm for 7 hours to produce Fe 3 O 4 Magnetic nanoparticles. Then, 2g of Fe 3 O 4 Dissolving magnetic micro-nano particles and 10g KH550 in 50mL of 75% ethanol aqueous solution by mass fraction, adding 4mL of triethylamine to adjust the pH value to 9, and condensing and refluxing for 10 hours at 110 ℃ to obtain aminated Fe 3 O 4 Micro-nano particles.
(2) PA610 was pretreated first with 50mL0.6wt% sodium carbonate solution at 60 ℃ for 1h and then with 220mL0.9mol/L HCl in a water bath at 55 ℃ for 4 h. 0.38g of pretreated PA610, 0.68g of glycidyl methacrylate, 0.62g of butyl methacrylate, 15mL of 45 vol% aqueous acetone solution and 50mg of benzoyl peroxide are added into a flask, and the mixture is continuously stirred and reacted at 75 ℃ for 5 hours at the rotating speed of 1000rpm under vacuum to form the nylon base material.
(3) 0.3g of the aminated Fe obtained in (1) 3 O 4 And (3) reacting the micro-nano particles, 6g of the nylon substrate material obtained in the step (2) and 0.6g of polyacrylic acid at normal temperature for 18 hours to obtain the carboxyl-containing nylon ferroferric oxide adsorbing material.
(4) And (3) carrying out lead ion adsorption performance test on the magnetic nylon adsorbing material containing carboxyl: preparing 60.5mg/L lead ion solution, putting 10mL into a small glass bottle, adjusting the pH value to 9, adjusting the temperature to 25 ℃, adding 26mg of adsorbing material, stirring for 3 hours, separating for 5min by a magnet, measuring the unit adsorption capacity of 18.161mg/g, the removal rate of 65.06 percent and the regeneration effect of 71.06 percent after 14 cycles.

Claims (8)

1. A preparation method of a carboxyl-containing nylon ferroferric oxide adsorbing material is characterized by comprising the following steps:
step one, fe 3 O 4 Preparation of magnetic micro-nano particles and Fe 3 O 4 Amino functionalization of the magnetic micro-nano particles;
step two, pretreating the nylon base material, and adding the pretreated nylon base material, acrylic monomers, an initiator and an acetone aqueous solution into a flask to prepare a nylon base material;
in the second step, firstly 0.2 to 0.6 weight percent of sodium carbonate solution is used for heating for 0.5 to 6 hours at the constant temperature of 60 ℃, and then 0.5 to 1.5mol/L of HCl is used for heating for 2 to 7 hours at the constant temperature of 55 ℃ in a constant temperature water bath to pre-treat the nylon base material; the nylon base material is PA6, PA66, PA11, PA12, PA1010, PA610 or PA612;
step three, carrying out amination on Fe obtained in the step one 3 O 4 And (3) carrying out composite reaction on the micro-nano particles, the nylon base material obtained in the step two and polyacrylic acid for 1-24 hours at normal temperature to obtain the carboxyl-containing nylon ferroferric oxide adsorbing material.
2. The preparation method of the carboxyl-containing nylon ferroferric oxide adsorbing material according to claim 1, wherein in the first step, fe 3 O 4 The preparation method of the magnetic micro-nano particles is a coprecipitation method, and comprises the following specific steps: feCl 3 ·6H 2 O、FeSO 4 ·7H 2 O, naOH and water are added into a flask in sequence, a mechanical stirrer and a thermometer are arranged, and the mixture is continuously stirred and reacted for 2 to 12 hours at the temperature of between 60 and 130 ℃ at the rotating speed of between 100 and 1000rpm to generate Fe 3 O 4 Magnetic micro-nano particles, feSO 4 ·7H 2 O、FeCl 3 ·6H 2 O, naOH and water in a mass ratio of 1:1 to 6:0.5 to 5:15 to 30.
3. The preparation method of the carboxyl-containing nylon ferroferric oxide adsorbing material according to claim 2, characterized in that in the step one, fe 3 O 4 The amino functionalization of the magnetic micro-nano particles specifically comprises the following steps: the prepared Fe 3 O 4 Dissolving the magnetic micro-nano particles and KH550 in 75% ethanol aqueous solution, adding triethylamine to adjust the pH value to 9, and carrying out condensation reflux at 80-110 ℃ for 6-10 h to obtain aminated Fe 3 O 4 Micro-nano particles; wherein, fe 3 O 4 The mass ratio of the magnetic micro-nano particles to the KH550 is 1:0.5 to 10.
4. The preparation method of a carboxyl-containing nylon ferroferric oxide adsorbing material according to claim 1, characterized in that in the second step, the pretreated nylon base material, the acrylic monomer, the initiator and the 40-50% by volume acetone aqueous solution are continuously stirred and reacted for 1-24 hours at a rotating speed of 100-1000 rpm under the conditions of vacuum and a temperature of 45-80 ℃ to obtain the nylon base material, wherein the mass ratio of the pretreated nylon base material, the acrylic monomer, the initiator and the 40-50% by volume acetone aqueous solution is 4-10: 5 to 80:1:150 to 300.
5. The preparation method of a carboxyl-containing nylon ferroferric oxide adsorbing material according to claim 1, wherein in the second step, the acrylic monomer comprises one or a combination of two or more of glycidyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, styrene, hydroxyethyl acrylate and hydroxypropyl acrylate.
6. The preparation method of a carboxyl-containing nylon ferroferric oxide adsorbing material according to claim 1, wherein in the second step, the initiator is benzoyl peroxide or azobisisobutyronitrile, and the mass ratio of the acrylic monomer to the initiator is 5-80: 1.
7. the preparation method of carboxyl-containing nylon ferroferric oxide adsorbing material according to claim 1, characterized in that in the third step, nylon base material and aminated Fe 3 O 4 The mass ratio of the micro-nano particles to the polyacrylic acid is 5-80: 1:0.5 to 8.
8. A carboxyl-containing nylon ferroferric oxide adsorbing material which is characterized by being prepared by the preparation method according to any one of claims 1 to 7.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870751A (en) * 2010-07-08 2010-10-27 河北工业大学 Method for preparing acrylic ester functionalized copolymer for plasticizing nylon 6
CN105017523A (en) * 2015-07-29 2015-11-04 苏州荣昌复合材料有限公司 Magnetic-adsorption nylon material
JP2017018843A (en) * 2014-03-17 2017-01-26 株式会社クラレ Water treatment method, water treatment polymer adsorbent, and regeneration method therefor
JP2017035660A (en) * 2015-08-10 2017-02-16 国立大学法人信州大学 Adsorption method of metal ion

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005058979A1 (en) * 2005-12-09 2007-06-21 Qiagen Gmbh Magnetic polymer particles
CN105170113B (en) * 2015-07-29 2017-07-11 中国地质大学（武汉） A kind of light-initiated method for preparing ionic composite magnetic particle adsorbent
US20180016162A1 (en) * 2016-07-15 2018-01-18 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Magnetic Metal Oxide Biochar Composite Particles, and Their Use in Recovering Pollutants From Aqueous Solution
US10689267B2 (en) * 2017-02-03 2020-06-23 The United States Of America, As Represented By The Secretary Of Agriculture Method for removing organic dyes from water using a hemoglobin/FE3O4 composite adsorbent
CN108160056B (en) * 2017-12-28 2020-12-18 大连海洋大学 Preparation method of nylon membrane for adsorbing heavy metals
CN112774641A (en) * 2021-01-12 2021-05-11 西安理工大学 Preparation method of carboxyl modified magnetic starch-based adsorption material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101870751A (en) * 2010-07-08 2010-10-27 河北工业大学 Method for preparing acrylic ester functionalized copolymer for plasticizing nylon 6
JP2017018843A (en) * 2014-03-17 2017-01-26 株式会社クラレ Water treatment method, water treatment polymer adsorbent, and regeneration method therefor
CN105017523A (en) * 2015-07-29 2015-11-04 苏州荣昌复合材料有限公司 Magnetic-adsorption nylon material
JP2017035660A (en) * 2015-08-10 2017-02-16 国立大学法人信州大学 Adsorption method of metal ion

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