CN103304820B - Preparation method of efficient polyethyleneimine modified cellulose-based heavy metal adsorbent - Google Patents
Preparation method of efficient polyethyleneimine modified cellulose-based heavy metal adsorbent Download PDFInfo
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Abstract
The invention discloses a preparation method of an efficient polyethyleneimine modified cellulose-based heavy metal adsorbent shown by a formula (I), belonging to the technical field of high-molecular function modification and synthesis of a natural material. By adopting cellulose as a framework, benzoyl peroxide (BPO) as an initiator, a mixture of water and acetone as a solvent and glycidyl methacrylate (GMA) shown by a formula (III) as a monomer, the method comprises the following steps of: performing a free radical-initiated graft copolymerization reaction on the surface of microcrystalline cellulose shown by a formula (II); performing amination on a graft product shown by a formula (IV) by use of graft polyethyleneimine (PEI) shown by a formula (V); and washing and drying the product to obtain a powdery solid product, wherein the reaction is easy to operate, and the conditions are mild. The heavy metal adsorbent prepared by the preparation method has the advantages of excellent adsorption property, large adsorption capacity and fast adsorption, can be regenerated and recycled, and has broad application prospects in the water treatment fields such as control of heavy metal industrial pollutants and the like.
Description
Technical field
The present invention relates to the preparation method of the imine modified cellulose base heavy metal absorbent of a kind of high-efficiency polyethylene, belong to the function modified technical field of natural macromolecular material.
Background technology
One metalloid element of heavy metal to be density be more than pure water five times, it increases in the exponential type of industry, agricultural, medical treatment and the multi-field application such as scientific and technological, its human contact's level is caused significantly to rise, excessive heavy metal will cause series of human disease, and heavy metal pollution of water body has become one of environmental problem the most serious in world wide.At present, from waste water, the method for heavy-metal ion removal is mainly: chemical precipitation method, membrane filter method, electrochemical process, ion exchange method, Coagulation Method, flotation process, adsorbent method.Advantages such as wherein adsorbent method is due to its advantages of good adsorption effect, has and does not produce secondary pollution, renewable recovery and obtain extensive concern.
Along with the raising of the reinforcement be familiar with the sustainable use of the energy and Environmental awareness, one of reproducible natural materials synthesis ideal chose becoming heavy metal absorbent.Wherein by cheap, easily preparation, degradable environmental-friendly natural macromolecular material---the sorbing material of Mierocrystalline cellulose synthesized by matrix becomes study hotspot.
Mierocrystalline cellulose is as macromolecular scaffold, there is good chemical stability and physical strength, molecular arrangement is closely orderly, and the cellulose crystallite district that strong hydrogen bond action is formed makes cellulosic polymer skeleton have certain intensity, anti swelling and chemical stability, it is also the important factor that graft modification with cellulose heavy metal absorbent can be recycled.But itself relatively low accessibility also limit its range of application while its higher mechanical property of imparting.In order to improve the functional of cellulose materials, investigators propose multiple modified method.
Grafting copolymerization process owing to neatly several functions group can be introduced cellulose skeleton, extreme enrichment modified effect and very attractive.Wherein, by introducing epoxide group fixed function group in grafting, copolymerization and modification process, because epoxy can wide, the good fixing effect of fixed function base scope and receiving much concern.The part but existing preparation method comes with some shortcomings, as epoxide group not acid and alkali-resistance, be difficult to ensure its epoxy group content while guarantee graft copolymerization percentage of grafting, constrain the fixed amount of functionalization group in unit sorbent material, finally have impact on the adsorption effect of sorbent material.Therefore, need to find a set of heavy metal absorbent preparation method ensureing grafting process epoxy group mass contg.
Summary of the invention
The object of the invention is by providing a set of new preparation method, significantly promoting the loading capacity of the macromolecule modified cellulose base heavy metal absorbent of gained, improving the monomer utilization ratio in macromolecule modified process simultaneously.
The invention provides the preparation method of the imine modified cellulose base heavy metal absorbent of high-efficiency polyethylene shown in formula (I), concrete preparation method comprises the steps:
In formula (I), formula (II) and formula (IV), n is 1,2,3,4... natural number; In formula (I) and formula (IV), m is 1,2, the natural number of 3...; In formula (I) and formula (V), p is 2,3,4.
Step (1), by the Microcrystalline Cellulose 50 DEG C of vacuum-dryings shown in 1g formula (II) to constant weight, is scattered in the mixed system of 5mL acetone and 10mL deionized water, at bath temperature 70 DEG C, stirs and lead to nitrogen deoxygenation 15min with magneton.
Step (2), adds initiator B PO and the monomer GMA shown in formula (III) in above-mentioned system, and logical nitrogen also keeps 70 DEG C, and constant temperature stops heating after stirring 2.5h.
Step (3), is cooled to after room temperature until system, obtains crude product by suction filtration, and washs it with deionized water and acetone.
Step (4), be the homopolymer produced in solvent removing reaction process with acetone, obtain the graft copolymer (Cell-g-PGMA) shown in formula (IV), at 50 DEG C, vacuum-drying is to constant weight.
Step (5), the PEI (molecular weight 600) shown in 0.504g formula (V) is dissolved in 20mL DMF (DMF), and strength of solution is 0.042mol.L
-1.
Step (6), adds step (5) gained solution by the Cell-g-PGMA shown in 1g formula (IV), passes into nitrogen protection, in 70 DEG C of constant temperature water bath heating 8h.
Step (7), with deionized water and the repeated multiple times washing step of dehydrated alcohol (6) products therefrom, to remove reaction solvent and unreacted polymine.Finally, carry out vacuum-drying to washing after product, at 50 DEG C, vacuum-drying is to constant weight, namely obtains the target affinity agent Cell-g-PGMA-PEI shown in formula (I).
In above-mentioned preparation method, the concentration range of the monomer GMA shown in step (2) formula used (III) is 3.8-19.2mmol.L
-1.
In above-mentioned preparation method, the Cell-g-PGMA percentage of grafting G shown in formula (IV) that step (6) is used
pbe 169%, grafting efficiency G
ebe 60.9%.
Below the principle of the inventive method is described as follows:
The preparation principle of the imine modified cellulose base heavy metal absorbent of high-efficiency polyethylene is: with the hydroxyl of cellulose surface for graft site, free radical is produced by chemical initiator benzoyl peroxide (BPO) decomposes, at main chain intermediate formation active site, further initiation vinyl monomer (III) (glycidyl methacrylate, GMA) be polymerized and grow side chain, side chain is connected with ehter bond with cellulosic backbone.Again with the epoxide group in the monomer GMA shown in formula (III) for the polymine (PEI) shown in function group and formula (V) reacts, namely the carbon atom in the primary amine in PEI, secondary amine nucleophilic attack epoxide group, epoxide group generation ring-opening reaction, PEI macromole is fixed on the cellulose graft copolymer (Cell-g-PGMA) shown in formula (IV), thus obtains the heavy metal absorbent (Cell-g-PGMA-PEI) shown in formula (I).
The preparation condition of the Cell-g-PGMA shown in formula (IV) is gentle, reaction process epoxy group group open loop phenomenon greatly reduces, thus ensure that the fixed amount of efficient heavy adsorption function compound PEI on graft copolymer, thus significantly improve the adsorption effect of sorbent material, as shown in Figure 1.
Excellent results of the present invention is as follows:
1. Mierocrystalline cellulose is cheap and easy to get, degradable, material toxicity are low, use safety, environmental protection.
2. adopt radical polymerization, reaction conditions is gentle, and high to the purity tolerance level of system, cost is low, easy to operate.
3. have employed the method for solution polymerization, mix and dispel the heat easy, production operation and temperature be all easy to control, and percentage of grafting and monomer conversion high.
4. adopt new synthesis route, ensure that the content of the epoxide group in graftomer, thus significantly improve the adsorption effect of such sorbent material.
5. heavy metal absorbent (Cell-g-PGMA-PEI) rate of adsorption is fast, and loading capacity is large, and reproducibility is good, can reuse.
Above-mentioned various features shows, the present invention is suitable for suitability for industrialized production, and is with a wide range of applications.
Accompanying drawing explanation
Heavy metal absorbent Cell-g-PGMA-PEI preparation flow figure shown in Fig. 1 formula (I) and adsorption effect figure (for cupric).
Heavy metal absorbent (Cell-g-PGMA-PEI) shown in Fig. 2 infrared (FT-IR) collection of illustrative plates (A) formula (I), the cellulose graft copolymer (Cell-g-PGMA) shown in (B) formula (IV), the Mierocrystalline cellulose shown in (C) formula (II).
The ultraviolet/visible light spectrophotometric analysis collection of illustrative plates of the Cell-g-PGMA-PEI complex compound shown in Fig. 3 Cu/ formula (I).
Embodiment
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
In the following embodiment of the present invention, (crystal grain diameter is 2.5 × 10 to reagent grade microcrystalline cellulose
-5m), glycidyl methacrylate (purity 98%), cladodification polymine (molecular weight 600, purity 99%), analytical pure benzoyl peroxide are all purchased from Aladdin reagent (Shanghai) Co., Ltd.; Analytical pure acetone is purchased from steel tower Reagent Company; Analytical pure hydrochloric acid is purchased from Beijing Chemical Plant; Analytical pure sodium hydroxide closes chemical reagent company limited purchased from three; Analytical pure dehydrated alcohol is purchased from Tianjin chemical reagent three factory; Analytical pure DMF is purchased from the special Chemical Company in Rui Jin, Tianjin.
The preparation of the glycidyl methacrylate graft modified-cellulose Cell-g-PGMA shown in embodiment 1. formula (IV)
(1) the 50 DEG C of vacuum-dryings of the Microcrystalline Cellulose shown in 1.0g formula (II) are to constant weight, are scattered in the mixed system of 5mL acetone and 10mL deionized water, bath temperature 70 DEG C, stir and lead to nitrogen deoxygenation 15min with magneton.
(2) in above-mentioned system, initiator B PO concentration 0.028mol.L is added
-1, the monomer GMA concentration 19.2mmol.L shown in formula (III)
-1, logical nitrogen also keeps 70 DEG C, and constant temperature stops heating after stirring 2.5h.
(3) be cooled to after room temperature until system, obtain crude product by suction filtration, and with deionized water and acetone, it is washed.
(4) be that solvent removes the homopolymer produced in reaction process with acetone, obtain the Cell-g-PGMA shown in formula (IV), at 50 DEG C, vacuum-drying is to constant weight.Calculate percentage of grafting G
pbe 169%, grafting efficiency G
ebe 60.9%.
As described in Example 1, difference is the GMA monomer concentration shown in change formula (III) is 15.1mmol.L to embodiment 2.
-1, calculate percentage of grafting G
pbe 150%, grafting efficiency G
ebe 69.9%.
As described in Example 1, difference is the GMA monomer concentration shown in change formula (III) is 11.3mmol.L to embodiment 3.
-1, calculate percentage of grafting G
pbe 99.9%, grafting efficiency G
ebe 62.1%.
As described in Example 1, difference is the GMA monomer concentration shown in change formula (III) is 7.6mmol.L to embodiment 4.
-1, calculate percentage of grafting G
pbe 55.0%, grafting efficiency G
ebe 51.3%.
As described in Example 1, difference is the GMA monomer concentration shown in change formula (III) is 3.8mmol.L to embodiment 5.
-1, calculate percentage of grafting G
pbe 18.0%, grafting efficiency G
ebe 33.6%.
The preparation of the cladodification polyethyleneimine-modified cellulose adsorbent Cell-PGMA-PEI shown in embodiment 6. formula (I)
(1) by the PEI (M shown in formula (V)
w=600) be dissolved in 20mL DMF, strength of solution is 0.042mol.L
-1.
(2) by Cell-g-PGMA (the percentage of grafting G shown in 1g formula (IV)
pbe 169%, grafting efficiency G
ebe 60.9%) add step (5) gained solution, pass into nitrogen protection, in 70 DEG C of constant temperature water bath heating 8h.
(3) crude product deionized water and the repeated multiple times washing of dehydrated alcohol, and vacuum-drying is carried out to washing after product, at 50 DEG C, vacuum-drying is to constant weight, namely obtains the target affinity agent Cell-g-PGMA-PEI shown in formula (I).
Claims (2)
1. the preparation method of the imine modified cellulose base heavy metal absorbent of the high-efficiency polyethylene shown in formula (I), with benzoyl peroxide (BPO) for initiator, the mixture selecting water and acetone is solvent, with the glycidyl methacrylate (GMA) shown in formula (III) for monomer, the graft copolymerization of free radical initiation is carried out on Microcrystalline Cellulose surface shown in formula (II), and carries out amination with the cladodification polymine PEI shown in formula (V) to the grafts shown in formula (IV); Concrete steps are as follows:
In formula (I), formula (II) and formula (IV), n is 1,2,3,4... natural number; In formula (I) and formula (IV), m is 1,2, the natural number of 3...; In formula (I) and formula (V), p is 2,3,4;
Step (1), by the Microcrystalline Cellulose 50 DEG C of vacuum-dryings shown in 1g formula (II) to constant weight, is scattered in the mixed system of 5mL acetone and 10mL deionized water, at bath temperature 70 DEG C, stirs and lead to nitrogen deoxygenation 15min with magneton;
Step (2), adds initiator B PO and the monomer GMA shown in formula (III) in above-mentioned system, and logical nitrogen also keeps 70 DEG C, and constant temperature stops heating after stirring 2.5h;
Step (3), is cooled to after room temperature until system, obtains crude product by suction filtration, and washs it with deionized water and acetone;
Step (4), be the homopolymer produced in solvent removing reaction process with acetone, obtain the graft copolymer Cell-g-PGMA shown in formula (IV), at 50 DEG C, vacuum-drying is to constant weight;
Step (5), the PEI being 600 by the molecular weight shown in 0.504g formula (V) is dissolved in 20mL DMF (DMF), and strength of solution is 0.042molL
-1;
Step (6), adds step (5) gained solution by the Cell-g-PGMA shown in 1g formula (IV), passes into nitrogen protection, in 70 DEG C of constant temperature water bath heating 8h;
Step (7), with deionized water and the repeated multiple times washing step of dehydrated alcohol (6) products therefrom, to remove reaction solvent and unreacted polymine; Finally, carry out vacuum-drying to washing after product, at 50 DEG C, vacuum-drying is to constant weight, namely obtains the target affinity agent Cell-g-PGMA-PEI shown in formula (I).
2. the preparation method of the imine modified cellulose base heavy metal absorbent of high-efficiency polyethylene shown in formula (I) as claimed in claim 1, is characterized in that, benzoyl peroxide (BPO) in step (2), concentration is 0.028molL
-1; Monomer methacrylic acid glycidyl ester (GMA) concentration shown in formula (III) is 19.2mmolL
-1, temperature of reaction is stabilized in 70 DEG C.
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