CN106268692A - 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 dimethylamine and modify porous magnetic dextran microspheres preparation method, it is characterised in that with petroleum ether, dichloromethane, octacosane as organic facies；Glucosan, nanometer Fe3O4Magnetic particle is aqueous phase；Aqueous phase is sprayed in organic facies, adds epoxychloropropane, lyophilization 24 h, obtain porous magnetic dextran microspheres；In the reactor, add by following composition mass percentage concentration, acetone: 64 ~ 70%, ethylenediamine: 2 ~ 8%, poly-epoxychloropropane dimethylamine: 8 ~ 14%, dissolve, porous magnetic dextran microspheres: 12 ~ 20%, each component sum is absolutely, in 50 ± 2 DEG C of constant temperature, stirring, back flow reaction 4 ~ 6h, after cooling, respectively with deionized water, washing with acetone, solid-liquid separation, it is dried, obtain poly-epoxychloropropane dimethylamine and modify porous magnetic dextran microspheres, this adsorbent has the highest adsorption capacity to bisphenol-A, Reusability is often, not only low cost but also environmental protection, there is magnetic simultaneously can be easily separated.
Description
Technical field
The present invention relates to the technical field of the preparation method of a kind of biological adsorption agent, particularly to a kind of Hydrin
Dimethylamine modifies porous magnetic dextran microspheres preparation method and the application technology adsorbing bisphenol-A (BPA).
Background technology
Poly-epoxychloropropane dimethylamine is a kind of new and effective water-soluble containing functional groups such as hydroxyl, amido, amine ions
Property cationic polymer, bisphenol-A in sewage is had extremely strong adsorption effect, but, directly using can be in water after treatment
Residual. therefore, in order to widen the range of choice of adsorbent further, improving adsorption effect, the application uses this polymer to many
Hole magnetic glucan micro-sphere carries out surface modification, opens up a new way for its application in sewage disposal.
Natural polymer magnetic microsphere is to grow up and be widely used to biomedicine, Chemical Decomposition enrichment in recent years
Deng a kind of Multifunction material in field, it has the characteristic of magnetic particle and polymer particles concurrently, it is convenient to from medium
Separating, the active group on macromolecule can load several functions molecule through modification simultaneously, to improve the selection of adsorbent
Property exceptional function, and due to it, there is good biocompatibility, thus multifunction magnetic microsphere can be prepared, in many fields
It is widely used.Porous dextran microspheres is a kind of soft gel microsphere with tridimensional network, has specific surface
The enzyme degradability etc. of long-pending big, good biocompatibility, hydrophilic and excellence, the slow release that generally can serve as medicine carries
Body, blood absorbence etc..The method of preparation porous dextran microspheres has a variety of at present, but great majority are by adding porogen
Preparing, the porogen added after having tested needs to extract from microsphere and obtain loose structure, the most not only
Make experiment loaded down with trivial details, and if porogen can not completely remove, the performance of porous microsphere can be produced certain impact.This Shen
Please glucosan plus nano Fe3O4Magnetic particle is aqueous phase, and with petroleum ether, octacosane as organic facies, epoxychloropropane is crosslinking
Agent, sorbitan fatty ester is dispersant, uses cryodesiccated method, prepares porous magnetic dextran microspheres.So
After use poly-epoxychloropropane dimethylamine modify.
In recent years, in water environment, the appearance of endocrine disruptor causes the extensive concern of people.Bisphenol-A (BPA) is wide
General for producing synthetic resin, plastics, synthetic fibers and pesticide.Meanwhile, BPA is again important environment incretion interferent,
It with the endogenous hormones estradiol competition binding estrogen receptor of human body, and can may cause a series of pathological changes, Long Term Contact
BPA can increase suffer from a heart complaint, diabetes and the risk of hepatopathy.Product containing BPA in use can be by all means
Entering environment thus endanger human health, if baby bottle is in Long Term Contact relatively hot liquid, BPA can gradually discharge thus right
Baby and the brain of child, behavior and prostate produce potential hazard.Therefore, federal government of Canada on October 18th, 2008
Announce, it is resolved that BPA is listed in noxious substance list.Therefore, drinking water in life and the waste water in commercial production are removed
BPA, is the important topic being related to the people's livelihood, is also the focus of domestic and international experts and scholars research.
Adsorbing separation removes organic and inorganic pollutant present in Environmental Water, has been considered as a kind of largely effective and normal
Processing method, the BPA using adsorption method of separation to remove in water becomes those skilled in the art's concerned issue.Use absorption point
From removing, BPA is existing to be reported, Liu Guifang etc. have studied bisphenol-A in Aqueous Solution on Modified Activated Carbons absorption (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
Study carefully sorption extraction stirring rod that molecularly imprinted polymer the is coating application (Lin Fu in environmental water sample content of bisphenol A measures
China etc., molecularly imprinted polymer is the application in environmental water sample content of bisphenol A measures of the sorption extraction stirring rod of coating, color
Spectrum, 2010,28(5): 507-512) Chinese patent CN 103418340 A discloses redox graphene-Fe3O4Nanometer is multiple
Condensation material and preparation method thereof and the application of absorption bisphenol-A；Chinese patent CN 102167371 B disclose a kind of modified beautiful
The preparation method of aluminum binary houghite and the application of bisphenol-A in adsorption treatment water body thereof.
When entering society, water pollution problems causes people more and more to pay close attention to.Along with day by day increasing the weight of of water pollution problems, system
Research emphasis has been become for strong points, high treating effect, the new material of repeatable utilization.Porous magnetic dextran microspheres is tool
Having the cancellated macromolecular compound in porous three-dimensional space, belong to soft gel, its micropore can suck a large amount of solvent, compares table
Area is big, and glucosan contains hydrophilic, also with dentates such as abundant hydroxyls, be easy to carry out chemical modification, porous magnetic
Dextran microspheres, i.e. belongs to natural polymer, can be with biodegradation, abundance environmental protection, can Reusability, there is again magnetic
Property easily from medium separate.It i.e. has the advantage of the good mechanical property of inorganic material, has again all excellent of organic material
Point, has no that poly-epoxychloropropane dimethylamine is modified porous magnetic dextran microspheres and prepared the report of adsorbent at present.Natural polymer
Sub-material is utilized as adsorbent and has the advantages such as renewable, degradable, environmental protection be friendly, cheap, is important living resources.
Summary of the invention
An object of the present invention is to provide a kind of poly-epoxychloropropane dimethylamine and modifies porous magnetic dextran microspheres system
Preparation Method, the poly-epoxychloropropane dimethylamine of acquisition is modified porous magnetic dextran microspheres adsorbent and is entered BPA in aqueous systems
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, it is characterised in that the party
Method has a following processing step:
(1) organic facies preparation: in the reactor, is added by following composition mass percentage concentration, petroleum ether: 50 ~ 58%, dichloromethane
Alkane: 26 ~ 32%, octacosane: 12 ~ 20%, each component sum is absolutely, stirs, for organic facies；
(2) aqueous phase preparation: in the reactor, is added by following composition mass percentage concentration, deionized water: 50 ~ 58%, glucosan:
32 ~ 40%, nanometer Fe3O4Magnetic particle: 4 ~ 10%, sodium hydroxide: 2 ~ 5%, each component sum is absolutely, ultrasonic disperse, for
Aqueous phase；
(3) preparation of porous magnetic dextran microspheres: in the reactor, at room temperature, under stirring with the speed of 2000 turns/min,
Being sprayed in the organic facies of step (1) by the aqueous phase of step (2), stirring reaction 1h, temperature rises to 60 ± 2 DEG C, adds volume hundred
Point concentration is the epoxychloropropane of 6 ~ 10%, continues reaction 8 ~ 10h, is cooled to room temperature, solid-liquid separation, fully washes with deionized water
Wash, be placed in plastic containers in-18 ~-20 DEG C of quick freeze, put into freeze drying box, lyophilization 24 h after taking-up, obtain
Porous magnetic dextran microspheres；
(4) poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, by forming matter as follows
Amount percentage concentration adds, acetone: 64 ~ 70%, ethylenediamine: 2 ~ 8%, and poly-epoxychloropropane dimethylamine: 8 ~ 14% dissolves, porous magnetic
Dextran microspheres: 12 ~ 20%, each component sum is absolutely, in 50 ± 2 DEG C of constant temperature, stirring, back flow reaction 4 ~ 6h, cooling
After, respectively by deionized water, washing with acetone, solid-liquid separation, it is dried, obtains poly-epoxychloropropane dimethylamine and modify porous magnetic Portugal
Polysaccharide microsphere, described poly-epoxychloropropane dimethylamine modifies the particle diameter of porous magnetic dextran microspheres between 40 ~ 100 μm.
Nanometer Fe described in step (2)3O4The particle diameter of magnetic particle is between 80 ~ 120nm.
The aqueous phase of step (2) is 1:1 with the volume ratio of the organic facies of step (1).
Poly-epoxychloropropane dimethylamine described in step (4) and porous magnetic dextran microspheres mass ratio 1:1.5 ~
It is optimum in the range of 2.0.
It is a further object of the present invention to provide poly-epoxychloropropane dimethylamine and modify porous magnetic dextran microspheres adsorbent
To absorption to BPA in aqueous systems, feature is: the poly-epoxychloropropane dimethylamine prepared is modified porous magnetic glucosan micro-
Ball adsorbent deionized water soaks 2 ~ 3h, adsorbs by static method.
The poly-epoxychloropropane dimethylamine prepared modification porous magnetic dextran microspheres adsorbent deionized water is soaked
Bubble 2 ~ 3h, is adsorbed by dynamic method.
The present invention compared with the prior art, has the advantage that and beneficial effect:
(1) the poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres adsorbent that the present invention obtains has good thing
Physicochemical stability and excellent mechanical strength, adsorption capacity is big, and the maximum adsorption capacity of BPA is reached 142.16 mg/g, wear-resisting
Can Reusability number of times up to more than 10 times, the speed of absorption is fast, and absorption chooses, and desorption performance is good, it is possible in wider acid
Use in the range of alkali.
(2) the poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres adsorbent that the present invention obtains both had had solid
The advantage of phase carrier material, also solves the losing issue that active group poly-epoxychloropropane dimethylamine is applied in water environment.
(3) good stability, is natural green product, regrown material, and garbage is biodegradable, has magnetic, easily from
Medium is separated.
(4) condition crossing range request synthesized is easily controlled, and energy consumption is low, simple to operate, belongs to process for cleanly preparing, it is easy to
Industrialized production.
Detailed description of the invention
Embodiment 1
(1) organic facies preparation: in the reactor, be separately added into, petroleum ether: 83mL, dichloromethane: 21mL, octacosane: 18g,
Stir, for organic facies；
(2) aqueous phase preparation: in the reactor, be separately added into, deionized water: 54mL, glucosan: 36g, nanometer Fe3O4Magnetic is micro-
Grain: 7g, sodium hydroxide: 3g, ultrasonic disperse, for aqueous phase；
(3) preparation of porous magnetic dextran microspheres: in the reactor, at room temperature, under stirring with the speed of 2000 turns/min,
Being sprayed in the organic facies of 100mL step (1) by the aqueous phase of 100mL step (2), stirring reaction 1h, temperature rises to 60 ± 2 DEG C,
Add epoxychloropropane 16mL, continue reaction 9h, be cooled to room temperature, solid-liquid separation, fully wash with deionized water, be placed in plastics
In-18 ~-20 DEG C of quick freeze in container, put into freeze drying box, lyophilization 24 h after taking-up, obtain porous magnetic Portugal
Polysaccharide microsphere；
(4) poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, is separately added into, third
Ketone: 86mL, ethylenediamine: 5.5mL, poly-epoxychloropropane dimethylamine: 10g, dissolve, and porous magnetic dextran microspheres: 17g, in 50
± 2 DEG C of constant temperature, stirring, back flow reaction 5h, after cooling, respectively by deionized water, washing with acetone, solid-liquid separation, be dried, gathered
Epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres.
Embodiment 2
(1) organic facies preparation: in the reactor, be separately added into, petroleum ether: 77mL, dichloromethane: 23mL, octacosane: 20g,
Stir, for organic facies；
(2) aqueous phase preparation: in the reactor, be separately added into, deionized water: 50mL, glucosan: 38g, nanometer Fe3O4Magnetic is micro-
Grain: 10g, sodium hydroxide: 2g, ultrasonic disperse, for aqueous phase；
(3) preparation of porous magnetic dextran microspheres: in the reactor, at room temperature, under stirring with the speed of 2000 turns/min,
Being sprayed in the organic facies of 100mL step (1) by the aqueous phase of 100mL step (2), stirring reaction 1h, temperature rises to 60 ± 2 DEG C,
Add epoxychloropropane 20mL, continue reaction 8h, be cooled to room temperature, solid-liquid separation, fully wash with deionized water, be placed in plastics
In-18 ~-20 DEG C of quick freeze in container, put into freeze drying box, lyophilization 24 h after taking-up, obtain porous magnetic Portugal
Polysaccharide microsphere；
(4) poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, is separately added into, third
Ketone: 26mL, ethylenediamine: 9mL, poly-epoxychloropropane dimethylamine: 8g, dissolve, and porous magnetic dextran microspheres: 20g, in 50 ± 2
DEG C constant temperature, stirring, back flow reaction 4h, after cooling, respectively by deionized water, washing with acetone, solid-liquid separation, be dried, obtain polycyclic
Oxygen chloropropane dimethylamine modifies porous magnetic dextran microspheres.
Embodiment 3
(1) organic facies preparation: in the reactor, be separately added into, petroleum ether: 85mL, dichloromethane: 24mL, octacosane: 14g,
Stir, for organic facies；
(2) aqueous phase preparation: in the reactor, be separately added into, deionized water: 52mL, glucosan: 40g, nanometer Fe3O4Magnetic is micro-
Grain: 5g, sodium hydroxide: 3g, ultrasonic disperse, for aqueous phase；
(3) preparation of porous magnetic dextran microspheres: in the reactor, at room temperature, under stirring with the speed of 2000 turns/min,
Being sprayed in the organic facies of 100mL step (1) by the aqueous phase of 100mL step (2), stirring reaction 1h, temperature rises to 60 ± 2 DEG C,
Add epoxychloropropane 15mL, continue reaction 10h, be cooled to room temperature, solid-liquid separation, fully wash with deionized water, be placed in and mould
In-18 ~-20 DEG C of quick freeze in material container, put into freeze drying box, lyophilization 24 h after taking-up, obtain porous magnetic
Dextran microspheres；
(4) poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, is separately added into, third
Ketone: 83mL, ethylenediamine: 4.5mL, poly-epoxychloropropane dimethylamine: 12g, dissolve, and porous magnetic dextran microspheres: 19g, in 50
± 2 DEG C of constant temperature, stirring, back flow reaction 5h, after cooling, respectively by deionized water, washing with acetone, solid-liquid separation, be dried, gathered
Epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres.
Embodiment 4
(1) organic facies preparation: in the reactor, be separately added into, petroleum ether: 85mL, dichloromethane: 24mL, octacosane: 14g,
Stir, for organic facies；
(2) aqueous phase preparation: in the reactor, be separately added into, deionized water: 58mL, glucosan: 32g, nanometer Fe3O4Magnetic is micro-
Grain: 6g, sodium hydroxide: 4g, ultrasonic disperse, for aqueous phase；
(3) preparation of porous magnetic dextran microspheres: in the reactor, at room temperature, under stirring with the speed of 2000 turns/min,
Being sprayed in the organic facies of 100mL step (1) by the aqueous phase of 100mL step (2), stirring reaction 1h, temperature rises to 60 ± 2 DEG C,
Add epoxychloropropane 18mL, continue reaction 9.5h, be cooled to room temperature, solid-liquid separation, fully wash with deionized water, be placed in and mould
In-18 ~-20 DEG C of quick freeze in material container, put into freeze drying box, lyophilization 24 h after taking-up, obtain porous magnetic
Dextran microspheres；
(4) poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, is separately added into, third
Ketone: 90mL, ethylenediamine: 2.5mL, poly-epoxychloropropane dimethylamine: 14g, dissolve, and porous magnetic dextran microspheres: 14g, in 50
± 2 DEG C of constant temperature, stirring, back flow reaction 5h, after cooling, respectively by deionized water, washing with acetone, solid-liquid separation, be dried, gathered
Epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres.
Embodiment 5
Weigh 0.20g poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres adsorbent and be placed in 250mL tool plug taper
Soaking 2 ~ 3 h in Ping, after filtration washing, adding 100mL concentration is in 400mg/LBPA standard solution, regulates body with diluted acid or alkali
In the range of the pH value of system is 2.0 ~ 11.0, at room temperature concussion absorption 2 ~ 6h, takes supernatant, electrochemically measures BPA's
Concentration, according to the concentration difference of BPA in water before and after absorption, calculates poly-epoxychloropropane dimethylamine modification porous magnetic glucosan micro-
The adsorption capacity of ball adsorbent, the poly-epoxychloropropane dimethylamine obtained by the present invention modifies the absorption of porous magnetic dextran microspheres
Agent is maximum and stable to the adsorption capacity of BPA to absorption pH value adsorbent in the range of 6.5 ~ 7.5 of BPA, at room temperature shakes
Swinging absorption 2h, BPA substantially to adsorb completely, the adsorption capacity of BPA is up to 142.16 mg/g.
Embodiment 6
Weigh 1.0g poly-epoxychloropropane dimethylamine modification porous magnetic dextran microspheres adsorbent and be placed in 250mL tool plug conical flask
Middle immersion 2 ~ 3 h, after filtration washing, adding 100mL concentration is in 200mg/LBPA standard solution, with diluted acid or alkali regulation system
PH value be 6.5 ~ 7.5 in the range of, at room temperature concussion absorption 4h, take supernatant, electrochemically measure the concentration of BPA,
According to the concentration difference of BPA in water before and after absorption, calculate poly-epoxychloropropane dimethylamine and modify the suction of porous magnetic dextran microspheres
The attached dose of clearance to BPA, the poly-epoxychloropropane dimethylamine obtained by the present invention modifies the absorption of porous magnetic dextran microspheres
Agent all more than 95.62%, reaches as high as 99% to the clearance of BPA.
Claims (5)
1. a poly-epoxychloropropane dimethylamine modifies porous magnetic dextran microspheres preparation method, it is characterised in that the method
There is following processing step:
(1) organic facies preparation: in the reactor, is added by following composition mass percentage concentration, petroleum ether: 50 ~ 58%, dichloromethane
Alkane: 26 ~ 32%, octacosane: 12 ~ 20%, each component sum is absolutely, stirs, for organic facies；
(2) aqueous phase preparation: in the reactor, is added by following composition mass percentage concentration, deionized water: 50 ~ 58%, glucosan:
32 ~ 40%, nanometer Fe3O4Magnetic particle: 4 ~ 10%, sodium hydroxide: 2 ~ 5%, each component sum is absolutely, ultrasonic disperse, for
Aqueous phase；
(3) preparation of porous magnetic dextran microspheres: in the reactor, at room temperature, under stirring with the speed of 2000 turns/min,
Being sprayed in the organic facies of step (1) by the aqueous phase of step (2), stirring reaction 1h, temperature rises to 60 ± 2 DEG C, adds volume hundred
Point concentration is the epoxychloropropane of 6 ~ 10%, continues reaction 8 ~ 10h, is cooled to room temperature, solid-liquid separation, fully washes with deionized water
Wash, be placed in plastic containers in-18 ~-20 DEG C of quick freeze, put into freeze drying box, lyophilization 24 h after taking-up, obtain
Porous magnetic dextran microspheres；
(4) poly-epoxychloropropane dimethylamine modifies the preparation of porous magnetic dextran microspheres, in the reactor, by forming matter as follows
Amount percentage concentration adds, acetone: 64 ~ 70%, ethylenediamine: 2 ~ 8%, and poly-epoxychloropropane dimethylamine: 8 ~ 14% dissolves, porous magnetic
Dextran microspheres: 12 ~ 20%, each component sum is absolutely, in 50 ± 2 DEG C of constant temperature, stirring, back flow reaction 4 ~ 6h, cooling
After, respectively by deionized water, washing with acetone, solid-liquid separation, it is dried, obtains poly-epoxychloropropane dimethylamine and modify porous magnetic Portugal
Polysaccharide microsphere, described poly-epoxychloropropane dimethylamine modifies the particle diameter of porous magnetic dextran microspheres between 40 ~ 100 μm.
2. modify porous magnetic dextran microspheres preparation side according to a kind of poly-epoxychloropropane dimethylamine described in claim 1
Method, it is characterised in that the nanometer Fe described in step (2)3O4The particle diameter of magnetic particle is between 80 ~ 120nm.
3. modify porous magnetic dextran microspheres preparation side according to a kind of poly-epoxychloropropane dimethylamine described in claim 1
Method, it is characterised in that the aqueous phase of rapid (2) is 1:1 with the volume ratio of the organic facies of step (1).
4. modify porous magnetic dextran microspheres preparation side according to a kind of poly-epoxychloropropane dimethylamine described in claim 1
Method, it is characterised in that the poly-epoxychloropropane dimethylamine described in step (4) and porous magnetic dextran microspheres mass ratio are 1:
It is optimum in the range of 1.5 ~ 2.0.
5. modify porous magnetic dextran microspheres preparation side according to a kind of poly-epoxychloropropane dimethylamine described in claim 1
Poly-epoxychloropropane dimethylamine prepared by method modifies porous magnetic dextran microspheres adsorbent.
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| CN106902755A (en) * | 2017-03-06 | 2017-06-30 | 济南大学 | A kind of preparation of the modified porous magnetic xanthans microballoon of 2 deracil |
| CN106944020A (en) * | 2017-03-06 | 2017-07-14 | 济南大学 | A kind of preparation method of modified porous magnetic xanthans/graphene complex microsphere |
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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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| CN106902755A (en) * | 2017-03-06 | 2017-06-30 | 济南大学 | A kind of preparation of the modified porous magnetic xanthans microballoon of 2 deracil |
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