CN106268692B - Poly-epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres preparation method - Google Patents
Poly-epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres preparation method Download PDFInfo
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Abstract
The invention discloses a kind of poly-epoxychloropropane dimethylamines to modify porous magnetic dextran microspheres preparation method, which is characterized in that using petroleum ether, dichloromethane, octacosane as organic phase；Glucan, nanometer Fe3O4Magnetic particle is water phase；Water is mutually sprayed in organic phase, adds in epoxychloropropane, 24 h is freeze-dried, obtains porous magnetic dextran microspheres；In the reactor, added in by following composition mass percentage concentration, acetone：64 ~ 70%, ethylenediamine：2 ~ 8%, poly-epoxychloropropane dimethylamine：8 ~ 14%, dissolving, porous magnetic dextran microspheres：12 ~ 20%, the sum of each component is absolutely, in 50 ± 2 DEG C of constant temperature, stirring, 4 ~ 6h of back flow reaction, after cooling, washed respectively with deionized water, acetone, separation of solid and liquid, it is dry, poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres are obtained, which has very high adsorption capacity to bisphenol-A, and Reusability is often, not only it is at low cost but also environmentally protective, while there is magnetism can be easily separated.
Description
Technical field
The present invention relates to a kind of technical field of the preparation method of biological adsorption agent, more particularly to a kind of Hydrin
The amine-modified porous magnetic dextran microspheres preparation method of diformazan and the application technology to bisphenol-A (BPA) absorption.
Background technology
Poly-epoxychloropropane dimethylamine is a kind of containing the new and effective water-soluble of the functional groups such as hydroxyl, amido, amine ion
Property cationic polymer, there is extremely strong adsorption effect to bisphenol-A in sewage, however, directly using in water after treatment
It remains therefore, in order to further widen the range of choice of adsorbent, improves adsorption effect, the application is using the polymer to more
Hole magnetic glucan micro-sphere is surface modified, and is opened up a new way for its application in sewage disposal.
Natural polymer magnetic microsphere is to grow up and be widely used to biomedical, Chemical Decomposition enrichment in recent years
A kind of novel and multifunctional material in the fields of grade, it has both the characteristic of magnetic particle and polymer particles, it is convenient to from medium
Separation, while the active group on macromolecule can load several functions molecule by modification, to improve the selection of adsorbent
The exceptional function of property, and since it is with good biocompatibility, so as to prepare multifunction magnetic microballoon, in many fields
It is widely used.Porous dextran microspheres are a kind of soft gel microballoons with tridimensional network, have specific surface
Big, the good biocompatibility of product, hydrophily and excellent enzyme degradability etc., the sustained release that usually may be used as drug carry
Body, blood absorbence etc..There are many kinds of the methods for preparing porous dextran microspheres at present, but most of is by adding pore-foaming agent
It is prepared, testing the pore-foaming agent added after finishing needs to extract from microballoon to obtain porous structure, so not only
Make experiment cumbersome, and certain influence can be generated to the performance of porous microsphere if pore-foaming agent cannot remove completely.This Shen
It please glucan plus nano Fe3O4Magnetic particle is water phase, and using petroleum ether, octacosane as organic phase, epoxychloropropane is crosslinking
Agent, sorbitan fatty ester are dispersant, using the method for freeze-drying, prepare porous magnetic dextran microspheres.So
It is modified afterwards using poly-epoxychloropropane dimethylamine.
In recent years, the appearance of endocrine disruptor causes the extensive concern of people in water environment.Bisphenol-A (BPA) is wide
It is general to be used to produce synthetic resin, plastics, synthetic fibers and pesticide.Meanwhile BPA is important environment incretion interferent again,
It and can may cause a series of lesions, Long Term Contact with the endogenous hormones estradiol competitive binding estrogen receptor of human body
BPA can increase suffer from a heart complaint, the risk of diabetes and hepatopathy.Product containing BPA in use can be by all means
Into environment so as to endanger human health, such as baby bottles in Long Term Contact compared in hot liquid, BPA can be gradually discharged so as to right
The brain of baby and children, behavior and prostate generate potential hazard.Therefore, federal government of Canada on October 18th, 2008
It announces, it is resolved that BPA is included in noxious material list.Therefore, the waste water in drinking water and industrial production in life is removed
BPA is the hot spot for the important topic and experts and scholars' research both at home and abroad for being related to the people's livelihood.
Adsorbing separation removes organic and inorganic pollutant present in ambient water, has been considered as a kind of largely effective and normal
Processing method, the BPA removed using adsorption method of separation in water become those skilled in the art's concerned issue.Using absorption point
Reported that Liu Guifang etc. has studied the absorption of bisphenol-A in Aqueous Solution on Modified Activated Carbons from BPA is removed（Liu Guifang etc.,
The absorption research of bisphenol-A in Aqueous Solution on Modified Activated Carbons, environmental science, 2008,29（2）：349-355）；Woods Fu Hua etc. is ground
Application of sorption extraction stirring rod of the molecularly imprinted polymer for coating in environmental water sample content of bisphenol A measure is studied carefully（Lin Fu
China etc., molecularly imprinted polymer for coating sorption extraction stirring rod environmental water sample content of bisphenol A measure in application, color
Spectrum, 2010,28（5）：507-512）Redox graphene-Fe is disclosed in 103418340 A of Chinese patent CN3O4Nanometer is multiple
Condensation material and preparation method thereof and the application for adsorbing bisphenol-A；It is disclosed in 102167371 B of Chinese patent CN a kind of modified beautiful
The preparation method of aluminum binary houghite and its in adsorption treatment water body bisphenol-A application.
When into society, water pollution problems causes people more and more to pay close attention to.With the increasingly exacerbation of water pollution problems, system
Standby with strong points, high treating effect, the repeatable new material utilized have become research emphasis.Porous magnetic dextran microspheres are tools
There is the high-molecular compound of porosity three-dimensional space net structure, belong to soft gel, micropore can suck a large amount of solvents, compare table
Area is big, and glucan contains hydrophily, also with dentates such as abundant hydroxyls, is easy to carry out chemical modification, porous magnetic
Dextran microspheres belong to natural polymer, can be biodegradable, and abundance is environmentally protective, can Reusability, and with magnetic
Property is easily separated from medium.It has the advantages that the good mechanical property of inorganic material, and all excellent with organic material
Point has no that poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres prepare the report of adsorbent at present.Natural polymer
Sub- material, which is utilized as adsorbent, to be had many advantages, such as renewable, degradable, environmentally friendly friendly, cheap, is important living resources.
The content of the invention
An object of the present invention is to provide a kind of poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres system
Preparation Method, acquisition poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres adsorbent in aqueous systems BPA into
Row adsorbing separation.
The purpose of the present invention is achieved through the following technical solutions.
A kind of poly-epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres preparation method, which is characterized in that the party
Method has following processing step：
（1）Organic phase is prepared：In the reactor, added in by following composition mass percentage concentration, petroleum ether：50 ~ 58%, two
Chloromethanes：26 ~ 32%, octacosane：12 ~ 20%, the sum of each component is organic phase absolutely, to stir evenly；
（2）Water is mutually prepared：In the reactor, added in by following composition mass percentage concentration, deionized water：50 ~ 58%, Portugal
Glycan：32 ~ 40%, nanometer Fe3O4Magnetic particle：4 ~ 10%, sodium hydroxide：2 ~ 5%, the sum of each component is absolutely, ultrasound divides
It dissipates, is water phase；
（3）The preparation of porous magnetic dextran microspheres：In the reactor, at room temperature, stirred with the speed of 2000 turns/min
It mixes down, by step（2）Water be mutually sprayed to step（1）Organic phase in, be stirred to react 1h, temperature rises to 60 ± 2 DEG C, adds in body
The epoxychloropropane that product percentage concentration is 6 ~ 10%, the reaction was continued 8 ~ 10h are cooled to room temperature, separation of solid and liquid is filled with deionized water
Divide washing, be placed in plastic containers in -18 ~ -20 DEG C of quick freezes, be put into after taking-up in freeze drying box, be freeze-dried 24 h,
Obtain porous magnetic dextran microspheres；
（4）Poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, by such as the following group
It is added in into mass percentage concentration, acetone：64 ~ 70%, ethylenediamine：2 ~ 8%, poly-epoxychloropropane dimethylamine：8 ~ 14%, dissolving is porous
Magnetic glucan micro-sphere：12 ~ 20%, the sum of each component is cold in 50 ± 2 DEG C of constant temperature, stirring, back flow reaction 4 ~ 6h for absolutely
But after, washed respectively with deionized water, acetone, separation of solid and liquid, it is dry, obtain poly-epoxychloropropane dimethylamine modification porous magnetic
Dextran microspheres, the poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres grain size 40 ~ 100 μm it
Between.
In step（2）Described in nanometer Fe3O4The grain size of magnetic particle is between 80 ~ 120nm.
Step（2）Water phase and step（1）Organic phase volume ratio be 1：1.
In step（4）Described in poly-epoxychloropropane dimethylamine and porous magnetic dextran microspheres mass ratio 1：1.5~
It is optimal in the range of 2.0.
It is a further object of the present invention to provide poly-epoxychloropropane dimethylamines to modify porous magnetic dextran microspheres adsorbent
To the absorption to BPA in aqueous systems, feature is：The poly-epoxychloropropane dimethylamine prepared modification porous magnetic glucan is micro-
Ball adsorbent impregnates 2 ~ 3h with deionized water, is adsorbed by static method.
The poly-epoxychloropropane dimethylamine prepared modification porous magnetic dextran microspheres adsorbent is soaked with deionized water
2 ~ 3h is steeped, is adsorbed by dynamic method.
The present invention compared with the prior art, has the following advantages that and advantageous effect：
（1）The poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres adsorbent that the present invention obtains has good
Physical and chemical stability and excellent mechanical strength, adsorption capacity is big, to the maximum adsorption capacity of BPA up to 142.16 mg/g,
It is wear-resisting can Reusability number up to 10 times or more, the speed of absorption is fast, and absorption chooses, and desorption performance is good, can be wider
Soda acid in the range of use.
（2）The poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres adsorbent that the present invention obtains both had had solid
The advantages of phase carrier material, also solves the losing issue that active group poly-epoxychloropropane dimethylamine is applied in water environment.
（3）Stability is good, is natural green product, and regrown material, discarded object is biodegradable, have magnetism, easily from
It is separated in medium.
（4）The condition for crossing range request of synthesis is easy to control, and low energy consumption, easy to operate, belongs to process for cleanly preparing, is easy to
Industrialized production.
Specific embodiment
Embodiment 1
（1）Organic phase is prepared：In the reactor, it is separately added into, petroleum ether：83mL, dichloromethane：21mL, octacosane：
18g is stirred evenly, and is organic phase；
（2）Water is mutually prepared：In the reactor, it is separately added into, deionized water：54mL, glucan：36g, nanometer Fe3O4It is magnetic
Particle：7g, sodium hydroxide：3g, ultrasonic disperse are water phase；
（3）The preparation of porous magnetic dextran microspheres：In the reactor, at room temperature, stirred with the speed of 2000 turns/min
It mixes down, by 100mL steps（2）Water be mutually sprayed to 100mL steps（1）Organic phase in, be stirred to react 1h, temperature rises to 60 ±
2 DEG C, epoxychloropropane 16mL, the reaction was continued 9h are added in, is cooled to room temperature, separation of solid and liquid is fully washed with deionized water, is placed in
It in -18 ~ -20 DEG C of quick freezes in plastic containers, is put into after taking-up in freeze drying box, is freeze-dried 24 h, obtains porous magnetic
Property dextran microspheres；
（4）Poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, adds respectively
Enter, acetone：86mL, ethylenediamine：5.5mL, poly-epoxychloropropane dimethylamine：10g, dissolving, porous magnetic dextran microspheres：17g,
In 50 ± 2 DEG C of constant temperature, stirring, back flow reaction 5h, after cooling, washed respectively with deionized water, acetone, separation of solid and liquid, it is dry, it obtains
Porous magnetic dextran microspheres are modified to poly-epoxychloropropane dimethylamine.
Embodiment 2
（1）Organic phase is prepared：In the reactor, it is separately added into, petroleum ether：77mL, dichloromethane：23mL, octacosane：
20g is stirred evenly, and is organic phase；
（2）Water is mutually prepared：In the reactor, it is separately added into, deionized water：50mL, glucan：38g, nanometer Fe3O4It is magnetic
Particle：10g, sodium hydroxide：2g, ultrasonic disperse are water phase；
（3）The preparation of porous magnetic dextran microspheres：In the reactor, at room temperature, stirred with the speed of 2000 turns/min
It mixes down, by 100mL steps（2）Water be mutually sprayed to 100mL steps（1）Organic phase in, be stirred to react 1h, temperature rises to 60 ±
2 DEG C, epoxychloropropane 20mL, the reaction was continued 8h are added in, is cooled to room temperature, separation of solid and liquid is fully washed with deionized water, is placed in
It in -18 ~ -20 DEG C of quick freezes in plastic containers, is put into after taking-up in freeze drying box, is freeze-dried 24 h, obtains porous magnetic
Property dextran microspheres；
（4）Poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, adds respectively
Enter, acetone：26mL, ethylenediamine：9mL, poly-epoxychloropropane dimethylamine：8g, dissolving, porous magnetic dextran microspheres：20g, in
50 ± 2 DEG C of constant temperature, stirring, back flow reaction 4h after cooling, are washed, separation of solid and liquid with deionized water, acetone respectively, dry, are obtained
Poly-epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres.
Embodiment 3
（1）Organic phase is prepared：In the reactor, it is separately added into, petroleum ether：85mL, dichloromethane：24mL, octacosane：
14g is stirred evenly, and is organic phase；
（2）Water is mutually prepared：In the reactor, it is separately added into, deionized water：52mL, glucan：40g, nanometer Fe3O4It is magnetic
Particle：5g, sodium hydroxide：3g, ultrasonic disperse are water phase；
（3）The preparation of porous magnetic dextran microspheres：In the reactor, at room temperature, stirred with the speed of 2000 turns/min
It mixes down, by 100mL steps（2）Water be mutually sprayed to 100mL steps（1）Organic phase in, be stirred to react 1h, temperature rises to 60 ±
2 DEG C, epoxychloropropane 15mL, the reaction was continued 10h are added in, is cooled to room temperature, separation of solid and liquid is fully washed with deionized water, put
It in -18 ~ -20 DEG C of quick freezes in plastic containers, is put into after taking-up in freeze drying box, is freeze-dried 24 h, obtains porous
Magnetic glucan micro-sphere；
（4）Poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, adds respectively
Enter, acetone：83mL, ethylenediamine：4.5mL, poly-epoxychloropropane dimethylamine：12g, dissolving, porous magnetic dextran microspheres：19g,
In 50 ± 2 DEG C of constant temperature, stirring, back flow reaction 5h, after cooling, washed respectively with deionized water, acetone, separation of solid and liquid, it is dry, it obtains
Porous magnetic dextran microspheres are modified to poly-epoxychloropropane dimethylamine.
Embodiment 4
（1）Organic phase is prepared：In the reactor, it is separately added into, petroleum ether：85mL, dichloromethane：24mL, octacosane：
14g is stirred evenly, and is organic phase；
（2）Water is mutually prepared：In the reactor, it is separately added into, deionized water：58mL, glucan：32g, nanometer Fe3O4It is magnetic
Particle：6g, sodium hydroxide：4g, ultrasonic disperse are water phase；
（3）The preparation of porous magnetic dextran microspheres：In the reactor, at room temperature, stirred with the speed of 2000 turns/min
It mixes down, by 100mL steps（2）Water be mutually sprayed to 100mL steps（1）Organic phase in, be stirred to react 1h, temperature rises to 60 ±
2 DEG C, epoxychloropropane 18mL, the reaction was continued 9.5h are added in, is cooled to room temperature, separation of solid and liquid is fully washed with deionized water, put
It in -18 ~ -20 DEG C of quick freezes in plastic containers, is put into after taking-up in freeze drying box, is freeze-dried 24 h, obtains porous
Magnetic glucan micro-sphere；
（4）Poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, adds respectively
Enter, acetone：90mL, ethylenediamine：2.5mL, poly-epoxychloropropane dimethylamine：14g, dissolving, porous magnetic dextran microspheres：14g,
In 50 ± 2 DEG C of constant temperature, stirring, back flow reaction 5h, after cooling, washed respectively with deionized water, acetone, separation of solid and liquid, it is dry, it obtains
Porous magnetic dextran microspheres are modified to poly-epoxychloropropane dimethylamine.
Embodiment 5
It weighs 0.20g poly-epoxychloropropane dimethylamines modification porous magnetic dextran microspheres adsorbent and is placed in 250mL tool plugs
2 ~ 3 h are impregnated in conical flask, after filtration washing, 100mL concentration are added in as in 400mg/LBPA standard solution, with diluted acid or alkali tune
The pH value of section system is in the range of 2.0 ~ 11.0, and 2 ~ 6h of concussion absorption, takes supernatant, electrochemically measure at room temperature
The concentration of BPA according to the concentration difference of BPA in water before and after absorption, calculates poly-epoxychloropropane dimethylamine modification porous magnetic Portugal
The adsorption capacity of glycan microsphere adsorbing agent, the poly-epoxychloropropane dimethylamine modification porous magnetic glucan obtained by the present invention are micro-
To the absorption pH value of BPA, the adsorbent in the range of 6.5 ~ 7.5 is maximum to the adsorption capacity of BPA and stablizes for ball adsorbent, in room
2h is adsorbed in the lower concussion of temperature, and BPA is adsorbed completely substantially, and the adsorption capacity of BPA is up to 142.16 mg/g.
Embodiment 6
It weighs 1.0g poly-epoxychloropropane dimethylamines modification porous magnetic dextran microspheres adsorbent and is placed in 250mL tool plug cones
2 ~ 3 h are impregnated in shape bottle, after filtration washing, add in 100mL concentration in 200mg/LBPA standard solution, to be adjusted with diluted acid or alkali
The pH value of system is in the range of 6.5 ~ 7.5, and concussion absorption 4h, takes supernatant at room temperature, electrochemically measures the dense of BPA
Degree according to the concentration difference of BPA in water before and after absorption, calculates poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres
Adsorbent is to the removal rate of BPA, the poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres suction obtained by the present invention
The attached dose of removal rate to BPA all more than 95.62%, reaches as high as 99%.
Claims (5)
1. a kind of poly-epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres preparation method, which is characterized in that this method
With following processing step：
(1) organic phase is prepared：In the reactor, added in by following composition mass percentage concentration, petroleum ether：50~58%, dichloro
Methane：26~32%, octacosane：12~20%, the sum of each component is organic phase absolutely, to stir evenly；
(2) water is mutually prepared：In the reactor, added in by following composition mass percent, deionized water：50~58%, glucan：
32~40%, nanometer Fe3O4Magnetic particle：4~10%, sodium hydroxide：2~5%, the sum of each component mass percent is percentage
Hundred, ultrasonic disperse, be water phase；
(3) preparation of porous magnetic dextran microspheres：In the reactor, at room temperature, under being stirred with the speed of 2000 turns/min,
The water of step (2) is mutually sprayed in the organic phase of step (1), is stirred to react 1h, temperature rises to 60 ± 2 DEG C, adds in volume hundred
Point concentration is 6~10% epoxychloropropane, the reaction was continued 8~10h, is cooled to room temperature, separation of solid and liquid is abundant with deionized water
Washing, is placed in plastic containers in -18~-20 DEG C of quick freezes, is put into after taking-up in freeze drying box, and freeze-drying for 24 hours, obtains
To porous magnetic dextran microspheres；
(4) preparation of poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres, in the reactor, by following composition matter
It measures percentage to add in, acetone：64~70%, ethylenediamine：2~8%, poly-epoxychloropropane dimethylamine：8~14%, dissolving is porous
Magnetic glucan micro-sphere：12~20%, the sum of each component mass percent is a hundred percent, in 50 ± 2 DEG C of constant temperature, stirring, is returned
Stream 4~6h of reaction, after cooling, is washed, separation of solid and liquid with deionized water, acetone respectively, dry, obtains Hydrin diformazan
Amine-modified porous magnetic dextran microspheres, the poly-epoxychloropropane dimethylamine modify the grain size of porous magnetic dextran microspheres
Between 40~100 μm.
2. according to a kind of poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres preparation side described in claim 1
Method, which is characterized in that the nanometer Fe described in step (2)3O4The grain size of magnetic particle is between 80~120nm.
3. according to a kind of poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres preparation side described in claim 1
Method, which is characterized in that the volume ratio of the water phase of step (2) and the organic phase of step (1) is 1：1.
4. according to a kind of poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres preparation side described in claim 1
Method, which is characterized in that the poly-epoxychloropropane dimethylamine described in step (4) is with porous magnetic dextran microspheres mass ratio 1：
1.5~2.0.
5. according to a kind of poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres preparation side described in claim 1
Poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres adsorbent prepared by method.
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| CN1986044A (en) * | 2006-11-30 | 2007-06-27 | 山东大学 | Polyepoxy chloropropane dimethylamine cationic bentonite and its preparing method |
| CN101254454A (en) * | 2007-12-10 | 2008-09-03 | 山东大学 | Preparation of epicholorohydrin-dimethylamine kation alta-mud grain |
| CN101759882A (en) * | 2008-12-25 | 2010-06-30 | 陕西北美基因股份有限公司 | Sephadex magnetic composite particles and preparation and use thereof |
| CN105195099A (en) * | 2015-09-21 | 2015-12-30 | 济南大学 | Preparation method of beta-cyclodextrin modified macroporous amino glucan adsorbent |
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| CN1986044A (en) * | 2006-11-30 | 2007-06-27 | 山东大学 | Polyepoxy chloropropane dimethylamine cationic bentonite and its preparing method |
| CN101254454A (en) * | 2007-12-10 | 2008-09-03 | 山东大学 | Preparation of epicholorohydrin-dimethylamine kation alta-mud grain |
| CN101759882A (en) * | 2008-12-25 | 2010-06-30 | 陕西北美基因股份有限公司 | Sephadex magnetic composite particles and preparation and use thereof |
| CN105195099A (en) * | 2015-09-21 | 2015-12-30 | 济南大学 | Preparation method of beta-cyclodextrin modified macroporous amino glucan adsorbent |
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