CN105236532A - Preparation method of microcrystalline cellulose/gamma-polyglutamic acid-nano silver composite material - Google Patents
Preparation method of microcrystalline cellulose/gamma-polyglutamic acid-nano silver composite material Download PDFInfo
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- CN105236532A CN105236532A CN201510629800.4A CN201510629800A CN105236532A CN 105236532 A CN105236532 A CN 105236532A CN 201510629800 A CN201510629800 A CN 201510629800A CN 105236532 A CN105236532 A CN 105236532A
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- microcrystalline cellulose
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- polyglutamic acid
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Abstract
The invention discloses a preparation method of a microcrystalline cellulose/gamma-polyglutamic acid-nano silver composite material. The preparation method comprises the following steps: pre-processing microcrystalline cellulose, dipping microcrystalline cellulose in silver salts, then adding a reducing agent into the mixed system to carry out reduction, carrying out centrifugal separation, washing the solids until the solids become neutral, drying the solids, dipping the solids in a gamma-polyglutamic acid solution, and carrying out crosslinking reactions between cellulose molecules and gamma-polyglutamic acid in the presence of carbodiimide to obtain the composite material. In the provided composite material, a certain amount of gamma-polyglutamic acid is crosslinked, the bactericidal effect of silver ions can be exerted, and the flocculation effect of gamma polyglutamic acid is also exerted. The prepared microcrystalline cellulose/gamma-polyglutamic acid-nano silver composite material can be used in the water treatment filed.
Description
Technical field
To the invention belongs to gamma-polyglutamic acid-modified microcrystalline cellulose and in the technology, particularly a kind of preparation method of Microcrystalline Cellulose/gamma-polyglutamic acid--nano composite material of its surface deposition nano particle.
Background technology
Water treatment is the focus of research both at home and abroad always.A large amount of use inorganic flocculating agent or have common machine polymeric flocculant to carry out water treatment as water purification agent can cause disadvantageous effect to human health, secondary pollution is caused to ecotope.Microbial material is adopted to produce this series products significant.
Nanometer silver is particle diameter is nano level elemental silver, has strong killing action to microorganisms such as various bacteria, fungi, spores, by widely in antibacterial, sterilizing field.Independent nanometer silver is easily reunited, and is often carried on other materials.Microcrystalline Cellulose is by part depolymerization, purified Mierocrystalline cellulose.Belong to straight chain formula polysaccharose substance.Be widely used in fields such as makeup, pharmacy, food.
Gamma-polyglutamic acid-is a kind of water-soluble, and not containing the biopolymer of toxicity, molecular weight from 5 ten thousand to 2 hundred ten thousand not etc., has very strong adsorption to various heavy positively charged ion, has good biodegradability simultaneously.Have a wide range of applications.Current Mierocrystalline cellulose loading nano silvery, and polyglutamic acid is as the report of water purification agent.But these work report large mainly with simple gamma-polyglutamic acid-as biological flocculant, using Mierocrystalline cellulose loading nano silvery as fungistat, act on more single.Not yet there is the research both combined at present.We have invented a kind of water purification agent gamma-polyglutamic acid-and Microcrystalline Cellulose-nano silver composite material are cross-linked.Compare the effect using respectively and can play better flocculation and sterilization, more preferably effect is played to water treatment.
Document 1 (Chen Xiaoli; The tall .SiO of Wei Li
2the preparation and property [J] of carrying nano silver antimicrobial powder. Chinese powder technology, 2013.) report one with SiO
2for the preparation method of the nano-silver antimicrobial powder of carrier, prepare the antimicrobial powder with general germ resistance.
Document 2 (Zhang Nianchun, Ao Yuyin, Ding Enyong, etc. Syntheses in water nanometer silver/nano micro crystal cellulose mixture and anti-microbial property [J] thereof. investigation of materials and application, 2014:160-164.) to report a kind of Microcrystalline Cellulose that adopts be the method that antiseptic-germicide is prepared in substrate.Nano silver particles appendix on nano micro crystal cellulose surface, effectively can be prevented the reunion of nanometer silver by it.
Document 3 (Ju Lei, Ma Xia. the flocculation activity research [J] of gamma-polyglutamic acid-. Shanghai Institute Of Technology's journal: natural science edition, 2011,11:30-33.) report the gamma-polyglutamic acid flocculating agent that a kind of fermentable obtains.It presents excellent throwing out in kaolin solution.It is a kind of Green Water Treatment Reagents.
There is following defect in the material of above-mentioned bibliographical information:
(1) antimicrobial powder of document 1 preparation is with SiO
2for carrier, have good germ resistance, but easily agglomeration occurs in water, utilization ratio reduces.
(2) preparation method that document 2 is reported uses the method reduction silver of ultrasonic reduction, can not completely by silver ion reduction.
(3) water purification agent that document 3 is reported has good flocculating function, is the water conditioner of efficient green, but functional more single, does not suppress the effect of the etiologies such as bacterium in water body.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method.
The technical solution realizing the object of the invention is: a kind of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method, comprises the following steps:
The first step, after Microcrystalline Cellulose is water-soluble, carry out supersound process, then adds silver salt solution, and at 20-80 DEG C, constant temperature stirs;
Second step, drip in the system of the first step reductive agent be carried out at 0-6 DEG C at reduction reaction;
3rd step, is warming up to room temperature by the reaction system of second step, then leaves standstill;
4th step, by the 3rd step products therefrom centrifugation, washs with ethanolic soln with after deionized water wash to neutrality again, obtains Microcrystalline Cellulose-nano silver composite material after drying;
5th step, obtains product and is placed in gamma-polyglutamic acid-solution and carries out dip treating by the 4th step;
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, the moisture in removing system;
7th step, carries out crosslinking reaction after being mixed by linking agent obtain Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material with the 6th step product.
In the first step, the molecular weight of Microcrystalline Cellulose is 200-1000; Silver salt is Silver Nitrate or Sulfuric acid disilver salt, and silver salt solution concentration is 0.002-0.6mol/L; The consumption mass ratio of silver salt and Microcrystalline Cellulose is 0.001:1-0.6:1; Churning time is 20-100 hour.
In second step, reductive agent is sodium borohydride, any one in hydrazine hydrate or formaldehyde.
In 3rd step, time of repose is 1-6 hour.
In 4th step, drying temperature is 45-100 DEG C, and time of drying is 10-65 hour.
In 5th step, gamma-polyglutamic acid-strength of solution is 0.008-6wt%, and the dip treating time is 15-24 hour; Gamma-polyglutamic acid-molecular weight is 7*10
5-2*10
6.
In 6th step, freezing temp is-15 ~-55 DEG C, and sublimation drying is 1-6 hour.
In 7th step, linking agent is the mixing of one or more in dicyclohexylcarbodiimide, glutaraldehyde, epoxy chloropropane, the consumption of linking agent is the 0.1-5.5% of Microcrystalline Cellulose quality, and crosslinking reaction temperature is 20-85 DEG C, and cross-linking reaction time is 0.5-24 hour.
Compared with prior art, its remarkable advantage is in the present invention:
(1) gamma-polyglutamic acid-through with Microcrystalline Cellulose-nano silver composite material crosslinking reaction after, impart the effect that flocculation agent sterilizing is antibacterial, most of impurity and bacterium in water body can be removed, water quality is improved.Simultaneously, nano silver particles, because load is on Microcrystalline Cellulose, solves the problem that nanoparticle is easily reunited, and can be dispersed in water uniformly and stably during rear matrix material purifying water body crosslinked with gamma-polyglutamic acid-, improve the utilization ratio of nanometer silver, reduce production cost.
(2) adopt nontoxic material as carrier, be suitable for water treatment
(3) only adopting biodegradable material, can not cause secondary pollution to environment, is eco-friendly water purification agent.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention.
Fig. 2 is cellulose-nano silver composite material XPS collection of illustrative plates, and a is full spectrum, b is the narrow spectrogram of Ag element.
Fig. 3 is trickle crystalline cellulose/gamma-polyglutamic acid--nano silver composite material XPS collection of illustrative plates.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Composition graphs 1, Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention, comprises the following steps:
The first step, after Microcrystalline Cellulose is water-soluble, carries out supersound process, and the molecular weight of Microcrystalline Cellulose is 200-1000.Add silver salt solution, Silver Nitrate or Sulfuric acid disilver salt, silver salt solution concentration is 0.002-0.6mol/L.Stir under constant temperature, whipping temp is 20-80 DEG C, and churning time is 20-100 hour;
Second step, adds reductive agent reduction in the system of the first step; Reductive agent is sodium borohydride, and the one in hydrazine hydrate or formaldehyde, dropwise operation temperature is 0-6 DEG C.
3rd step, is warming up to room temperature naturally by the reaction system of second step, then leaves standstill 1-6 hour;
4th step, by the 3rd step products therefrom centrifugation, with after deionized water wash 3-5 time again with ethanolic soln washing 1-3 time, obtain Microcrystalline Cellulose-nano silver composite material after drying, drying temperature is 45-100 DEG C, and the time is 10-65 hour;
5th step, by the 4th step product be placed in gamma-polyglutamic acid-and carry out dip treating, gamma-polyglutamic acid-strength of solution is 0.008-6%, and gamma-polyglutamic acid-molecular weight is 7*10
5-2*10
6;
6th step, after being separated by filtration by the 5th step products therefrom, carry out lyophilize, the moisture in the system of going out, freezing temp is-15---55 DEG C, sublimation drying is 1-6 hour, removes the moisture of wherein 30-65%;
7th step, carry out crosslinking reaction after being mixed with the 6th step product by linking agent, linking agent is the mixing of one or more in Carbodiimides, glutaraldehyde, epoxy chloropropane, and the consumption of linking agent is cellulosic 0.1-5.5%, temperature of reaction is 20-85 DEG C, and the reaction times is 0.5-24 hour;
8th step, after the 7th step product is done rotproofing, obtains Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material
The present invention, Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method, the consumption mass ratio of silver salt and Microcrystalline Cellulose is 0.001:1-0.6:1.
As shown in Figure 2, Microcrystalline Cellulose-nano silver composite material surface only has C, O, Ag tri-kinds of elements to illustrate, and also prepared material is pure, do not have impurity.Calculating massfraction shared by Ag element by peak area and each atomic sensitivity factor is 13.7%.Right figure is the narrow spectrogram of Ag, and correspondence Ag3d5/2 and Ag3d3/2 spin orbital is distinguished at the peak of 368.3eV, 374.3eV, completely the same with the peak of elemental silver.Silver in interpret sample only exists with the state of silver-colored simple substance.
As shown in Figure 3, be cross-linked with gamma-polyglutamic acid-in rear XPS collection of illustrative plates and occurred that N peak derives from the amino in gamma-polyglutamic acid-.
Employing standard Plating counts bacterium in water sample, and the sterilizing rate of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material is 99.8%
Below in conjunction with specific embodiment, the present invention is described in further detail.
Embodiment 1: Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention, comprises the following steps:
The first step, after water-soluble for 5g Microcrystalline Cellulose, carries out supersound process, and the molecular weight of Microcrystalline Cellulose is 200-1000.Add the AgNO of 0.6mol/L
3(25mL), at room temperature stir, churning time is 2-3 hour;
Second step, is placed in ice bath by the reaction system of the first step, and when temperature is lower than 5 DEG C, sodium borohydride (50mL) the whole reaction process starting to drip 0.2mol/L is no more than 5 DEG C.
3rd step, is warming up to room temperature naturally by the reaction system of second step, then leaves standstill 1-6 hour.
4th step, by the 3rd step products therefrom centrifugation, washs 1 time with ethanolic soln again with after deionized water wash 3 times, and in air, 85 DEG C of dryings 10 hours, obtain Microcrystalline Cellulose-nano silver composite material.
5th step, by the 4th step product to be placed in concentration be that 1% gamma-polyglutamic acid-carries out immersion 20h.
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, to go out in material 50% moisture.
7th step, be cross-linked at 45 DEG C after being mixed with the 6th step product by 1.5% carbodiimide cross-linker, the reaction times is 24 hours;
8th step, after the 7th step product is done rotproofing, obtains Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material
Embodiment 2: Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention, comprises the following steps:
The first step, after water-soluble for 5g Microcrystalline Cellulose, carries out supersound process, and the molecular weight of Microcrystalline Cellulose is 200-1000.Add the AgNO of 0.003mol/L
3(25mL), at room temperature stir, churning time is 2-3 hour;
Second step, is placed in ice bath by the reaction system of the first step, and when temperature is lower than 5 DEG C, sodium borohydride (1mL) the whole reaction process starting to drip 0.05mol/L is no more than 5 DEG C.
3rd step, with embodiment 1 the 3rd step;
4th step, by the 3rd step products therefrom centrifugation, washs 1 time with ethanolic soln again with after deionized water wash 3 times, and in air, 50 DEG C of dryings 24 hours, obtain Microcrystalline Cellulose-nano silver composite material.
5th step, by the 4th step product to be placed in concentration be that 2% gamma-polyglutamic acid-carries out immersion 15h.
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, to go out in material 40% moisture.
7th step, be cross-linked at 50 DEG C after being mixed with the 6th step product by 1.5% epichlorohydrin crosslinker, the reaction times is 16 hours;
8th step, after the 7th step product is done rotproofing, obtains Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material
Embodiment 3: Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention, comprises the following steps:
The first step, after water-soluble for 5g Microcrystalline Cellulose, carries out supersound process, and the molecular weight of Microcrystalline Cellulose is 200-1000.Add the Ag of 0.06mol/L
2sO
4(25mL), at room temperature stir, churning time is 1-2 hour;
Second step, is placed in ice bath by the reaction system of the first step, and when temperature is lower than 5 DEG C, sodium borohydride (10mL) the whole reaction process starting to drip 0.2mol/L is no more than 5 DEG C.
3rd step, with embodiment 1 the 3rd step;
4th step, by the 3rd step products therefrom centrifugation, washs 1 time with ethanolic soln again with after deionized water wash 4 times, and in air, 60 DEG C of dryings 20 hours, obtain Microcrystalline Cellulose-nano silver composite material.
5th step, by the 4th step product to be placed in concentration be that 0.5% gamma-polyglutamic acid-carries out immersion 24h.
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, to go out in material 30% moisture.
7th step, be cross-linked at 50 DEG C after being mixed with the 6th step product by 2.5% dicyclohexylcarbodiimide linking agent, the reaction times is 18 hours;
8th step, after the 7th step product is done rotproofing, obtains Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material.
Embodiment 4: Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention, comprises the following steps:
The first step, after water-soluble for 5g Microcrystalline Cellulose, carries out supersound process, and the molecular weight of Microcrystalline Cellulose is 200-1000.Add the AgNO of 0.05mol/L
3(25mL), at room temperature stir, churning time is 2-3 hour;
Second step, is placed in ice bath by the reaction system of the first step, and when temperature is lower than 5 DEG C, hydrazine hydrate (10mL) the whole reaction process starting to drip 0.1mol/L is no more than 5 DEG C.
3rd step, with embodiment 1 the 3rd step;
4th step, by the 3rd step products therefrom centrifugation, washs 2 times with ethanolic soln again with after deionized water wash 3 times, and in air, 50 DEG C of dryings 24 hours, obtain Microcrystalline Cellulose-nano silver composite material.
5th step, by the 4th step product to be placed in concentration be that 1% gamma-polyglutamic acid-carries out immersion 18h.
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, to go out in material 50% moisture.
7th step, be cross-linked at 45 DEG C after being mixed with the 6th step product by 3.5% dicyclohexylcarbodiimide linking agent, the reaction times is 18 hours;
8th step, after the 7th step product is done rotproofing, obtains Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material
Embodiment 5: Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention, comprises the following steps:
The first step, after water-soluble for 5g Microcrystalline Cellulose, carries out supersound process, and the molecular weight of Microcrystalline Cellulose is 200-1000.Add the AgNO of 0.05mol/L
3(25mL), at room temperature stir, churning time is 2-3 hour;
Second step, is placed in ice bath by the reaction system of the first step, and when temperature is lower than 5 DEG C, formaldehyde solution (5mL) the whole reaction process starting to drip 1mol/L is no more than 5 DEG C.
3rd step, with embodiment 1 the 3rd step;
4th step, by the 3rd step products therefrom centrifugation, washs 2 times with ethanolic soln again with after deionized water wash 4 times, and in air, 80 DEG C of dryings 16 hours, obtain Microcrystalline Cellulose-nano silver composite material.
5th step, by the 4th step product to be placed in concentration be that 4% gamma-polyglutamic acid-carries out immersion 20h.
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, to go out in material 50% moisture.
7th step, be cross-linked at 50 DEG C after 3% glutaraldehyde cross-linking agent being mixed with the 6th step product, the reaction times is 18 hours;
8th step, after the 7th step product is done rotproofing, obtains Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material
Embodiment 6: Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention, comprises the following steps:
The first step, after water-soluble for 5g Microcrystalline Cellulose, carries out supersound process, and the molecular weight of Microcrystalline Cellulose is 200-1000.Add 0.03mol/LAg
2sO
4(25mL), at room temperature stir, churning time is 2-3 hour;
Second step, is placed in ice bath by the reaction system of the first step, and when temperature is lower than 5 DEG C, sodium borohydride (50mL) the whole reaction process starting to drip 0.5mol/L is no more than 5 DEG C.
3rd step, with embodiment 1 the 3rd step;
4th step, by the 3rd step products therefrom centrifugation, washs 1 time with ethanolic soln again with after deionized water wash 3 times, and in air, 45 DEG C of dryings 48 hours, obtain Microcrystalline Cellulose-nano silver composite material.
5th step, by the 4th step product to be placed in concentration be that 4.5% gamma-polyglutamic acid-carries out immersion 18h.
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, to go out in material 60% moisture.
7th step, be cross-linked at 60 DEG C after being mixed with the 6th step product by 5% dicyclohexylcarbodiimide linking agent, the reaction times is 18 hours;
8th step, after the 7th step product is done rotproofing, obtains Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material.
Embodiment 7: Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material preparation method of the present invention, comprises the following steps:
The first step, after water-soluble for 5g Microcrystalline Cellulose, carries out supersound process, and the molecular weight of Microcrystalline Cellulose is 200-1000.Add 0.1mol/LAg
2sO
4(25mL), at room temperature stir, churning time is 2-3 hour;
Second step, is placed in ice bath by the reaction system of the first step, and when temperature is lower than 5 DEG C, sodium borohydride (50mL) the whole reaction process starting to drip 1mol/L is no more than 5 DEG C.
3rd step, with embodiment 1 the 3rd step;
4th step, by the 3rd step products therefrom centrifugation, washs 2 times with ethanolic soln again with after deionized water wash 5 times, and in air, 80 DEG C of dryings 10 hours, obtain Microcrystalline Cellulose-nano silver composite material.
5th step, by the 4th step product to be placed in concentration be that 2.5% gamma-polyglutamic acid-carries out immersion 24h.
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, to go out in material 60% moisture.
7th step, be cross-linked at 50 DEG C after being mixed with the 6th step product by 5.5% dicyclohexylcarbodiimide linking agent, the reaction times is 24 hours;
8th step, after the 7th step product is done rotproofing, obtains Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material.
Claims (8)
1. a preparation method for Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material, is characterized in that, comprise the following steps:
The first step, after Microcrystalline Cellulose is water-soluble, carry out supersound process, then adds silver salt solution, and at 20-80 DEG C, constant temperature stirs;
Second step, drip in the system of the first step reductive agent be carried out at 0-6 DEG C at reduction reaction;
3rd step, is warming up to room temperature by the reaction system of second step, then leaves standstill;
4th step, by the 3rd step products therefrom centrifugation, washs with ethanolic soln with after deionized water wash to neutrality again, obtains Microcrystalline Cellulose-nano silver composite material after drying;
5th step, obtains product and is placed in gamma-polyglutamic acid-solution and carries out dip treating by the 4th step;
6th step, after being separated by filtration by the 5th step products therefrom, carries out lyophilize, the moisture in removing system;
7th step, carries out crosslinking reaction after being mixed by linking agent obtain Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material with the 6th step product.
2. the preparation method of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material as claimed in claim 1, it is characterized in that, in the first step, the molecular weight of Microcrystalline Cellulose is 200-1000; Silver salt is Silver Nitrate or Sulfuric acid disilver salt, and silver salt solution concentration is 0.002-0.6mol/L; The consumption mass ratio of silver salt and Microcrystalline Cellulose is 0.001:1-0.6:1; Churning time is 20-100 hour.
3. the preparation method of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material as claimed in claim 1, it is characterized in that, in second step, reductive agent is sodium borohydride, any one in hydrazine hydrate or formaldehyde.
4. the preparation method of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material as claimed in claim 1, it is characterized in that, in the 3rd step, time of repose is 1-6 hour.
5. the preparation method of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material as claimed in claim 1, it is characterized in that, in the 4th step, drying temperature is 45-100 DEG C, and time of drying is 10-65 hour.
6. the preparation method of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material as claimed in claim 1, it is characterized in that, in the 5th step, gamma-polyglutamic acid-strength of solution is 0.008-6wt%, and the dip treating time is 15-24 hour; Gamma-polyglutamic acid-molecular weight is 7*10
5-2*10
6.
7. the preparation method of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material as claimed in claim 1, it is characterized in that, in the 6th step, freezing temp is-15 ~-55 DEG C, and sublimation drying is 1-6 hour.
8. the preparation method of Microcrystalline Cellulose/gamma-polyglutamic acid--nano silver composite material as claimed in claim 1, it is characterized in that, in 7th step, linking agent is the mixing of one or more in dicyclohexylcarbodiimide, glutaraldehyde, epoxy chloropropane, the consumption of linking agent is the 0.1-5.5% of Microcrystalline Cellulose quality, crosslinking reaction temperature is 20-85 DEG C, and cross-linking reaction time is 0.5-24 hour.
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| CN107265552A (en) * | 2017-08-16 | 2017-10-20 | 中国农业科学院麻类研究所 | The method that magnetic cellulose/polyglutamic acid coupling material removes Cr VI in waste water |
| CN107265552B (en) * | 2017-08-16 | 2019-07-19 | 中国农业科学院麻类研究所 | The method of Cr VI in magnetic cellulose/polyglutamic acid coupling material removal waste water |
| CN108723390A (en) * | 2018-05-28 | 2018-11-02 | 广东省微生物研究所（广东省微生物分析检测中心） | A kind of short-cut method preparing nano silver composite antibacterial agent |
| CN108723390B (en) * | 2018-05-28 | 2021-04-06 | 广东省微生物研究所（广东省微生物分析检测中心） | Simple method for preparing nano-silver composite antibacterial agent |
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