CN106632828A - Functional polymer microspheres, and preparation method and application thereof - Google Patents
Functional polymer microspheres, and preparation method and application thereof Download PDFInfo
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- CN106632828A CN106632828A CN201611066002.6A CN201611066002A CN106632828A CN 106632828 A CN106632828 A CN 106632828A CN 201611066002 A CN201611066002 A CN 201611066002A CN 106632828 A CN106632828 A CN 106632828A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F261/00—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00
- C08F261/02—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols
- C08F261/04—Macromolecular compounds obtained by polymerising monomers on to polymers of oxygen-containing monomers as defined in group C08F16/00 on to polymers of unsaturated alcohols on to polymers of vinyl alcohol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
Abstract
The invention discloses functional polymer microspheres which comprise the following elements in percentage by mass: 46.64% of C, 7.93% of H, 1.66% of N, 39.3% of O and 1.75% of S. The structural formula of the polymer microspheres is disclosed as Formula (I). The functional polymer microspheres have the characteristics of wide material sources, high economy, environment friendliness, easy modification, high adsorption efficiency and the like, and overcome the defects in the commercially available solid-phase extraction materials at present. When being used as a core filler for solid-phase extraction operation, the functional polymer microspheres can simultaneously implement separation and enrichment on thirteen heavy metal ions in the environmental water; the adsorption rates for copper, zinc, arsenic, cadmium, lead, mercury, tin and bismuth heavy metal ions are respectively 92% or above; and the adsorption rates for the other heavy metal ions (vanadium, chromium, cobalt, antimony and barium) can reach 50% or above. The method is simple and convenient to operate, has fast treatment effects, and has considerable application prospects in the field of inorganic pollutant separation analysis in the actual environmental water.
Description
Technical field
The present invention relates to inorganic pollution separate analytical technique field, and in particular to a kind of functional polymer microsphere and its system
Preparation Method and application, using the diversity of functional polymer microsphere, easily modification and the features such as environmental protection and economy, the functional polymer is micro-
Ball can simultaneously 13 heavy metal species ions in separation and concentration environment water.
Background technology
With industrial development, the pollution of heavy metal in environment is on the rise, and has had influence on the normal life of the mankind
It is living, and most metallic elements all show different degrees of toxicity, therefore, trace metal is especially weighed in accurate analysis environments water body
The content of metallic element is significant.But matrix effect can hinder semiochemical acquisition in actual sample, and
Target concentration is too low also to make semiochemical feature unobvious.By beneficiation technologies are efficiently separated, interference matrix is eliminated,
Target concentration is improved, is the important channel for accurately capturing effective information.And currently available sample separation and concentration is theoretical
Still it is difficult to meet the needs of all kinds of sample systems with method.Therefore, the new theory of sample pretreatment (separation and concentration), new side are set up
Method and detection technique, remain one of bottleneck of environmental analysis scientific development.SPE is a kind of important sample pretreatment
Technology, its basic characteristics are that reagent consumption is few, and enrichment times are high, and operating process is simple, and required expense is relatively low, it is often more important that its
Automation is easily realized, so as to getting the attention and paying attention to.Constantly develop new fiber material and in original material
Carry out appropriate modified to reaching more preferable effect of extracting on the basis of material, be the important development side of new solid phase extraction techniques
To.
Synthesis macromolecular material is one of mark of civilization of human society, has synthesized up to ten thousand kinds of macromolecular materials so far.
The macromolecular material of synthesis usually contains many function functional groups, can respectively with many kinds of metal ions with covalent bond, ionic bond,
Van der Waals force is combined, therefore, synthesize the separation and concentration that macromolecular material is widely used in Heavy Metals in Waters ion.Using height
The stable structure of molecular material and chemical property are improving the recycling rate of waterused of adsorbent；By macromolecular material and other are inorganic,
Organic material is combined the sorbing material made with high-specific surface area, high adsorption capacity；By the synthesis bar for controlling macromolecular material
Part and the species and quantity of functional group, realize the high selectivity and quick adsorption of heavy metal ion, so as to realize with it is most simple,
Effectively method reaches maximally utilizing for heavy metal resources.These will all be such that macromolecular material analyzes in separation of heavy metal ions
Field has very high potentiality to be exploited and using value.
In numerous macromolecular materials, globules of cross-linked polymers extensively applied environment protection, chromatographic isolation, biochemistry and can have
The multiple fields such as the separation of machine compound.Globules of cross-linked polymers can be divided into gel-type and macroporous type, and wherein macroporous type crosslinking is poly-
Compound bead has permanent loose structure, though also there is very big surface area in dry state, and macroporous type cross-linked polymeric
Thing bead is more higher than gel-type globules of cross-linked polymers adsorption capacity, when chemical modification is carried out, it is easier to obtain high function
Base introducing rate.
At present, the shortcomings of commercially available solid phase extraction filler generally existing is selective not enough, repeatability is bad and expensive.This
Invention is by the use of cheap acrylate monomer and propenoic acid dialkyl amido ethyl ester monomer as reaction monomers, acrylic acid
Esters are crosslinking agent, while add a certain proportion of pore-foaming agent to prepare porous crosslinked polymeric bead, using propyl sulfonic acid lactone
Modification obtains the functional polymer microsphere that surface-active site is evenly distributed.Using functional polymer microsphere as solid-phase extraction column
Core filler, can fast and effeciently copper that may be present in separation and concentration environment water, zinc, arsenic, cadmium, lead, mercury, tin, bismuth,
Vanadium, chromium, cobalt, antimony, the heavy metal species ion of barium 13.
The content of the invention
In view of this, it is an object of the invention to propose a kind of functional polymer microsphere, the functional polymer microsphere has
The many advantages such as efficiently, environmentally friendly, selective good and strong antijamming capability, and can be used as the core filler of solid-phase extraction column, energy
Copper that may be present in enough fast and effeciently separation and concentration environment waters, zinc, arsenic, cadmium, lead, mercury, tin, bismuth, vanadium, chromium, cobalt, antimony,
The heavy metal species ion of barium 13, it is considerable in the using value of field of environment protection.
Based on a kind of functional polymer microsphere that above-mentioned purpose, the present invention are provided, each element in the polymer microballoon
Mass percent is as follows：C:46.64%, H:7.93%, N:1.66%, O:39.3%, S:1.75%；The polymer microballoon
Shown in structural formula such as formula (I)：
Analysis of physical and chemical property is carried out to resulting functional polymer microsphere, adopts densitometer to determine its density for 0.98.
C is measured using elemental analyser, H, N, O mass percent is C：46.64%, H：7.93%, N：1.66%, O：39.3%；Adopt
With inductively-coupled plasma spectrometer S contents are measured for 1.75%.Using Fourier infrared spectrograph and ESEM (SEM)
Functional polymer microsphere structure and morphology characterization are carried out, as can be seen that 530cm from infrared spectrum-1,620cm-1,1068cm-1
And 1190cm-1Locate as sulfonic characteristic absorption peak, and 1730cm-1Then inhale for the C=O stretching vibrations of methacrylate at place
Receive peak；The prepared functional polymer microsphere particle diameter distribution of ESEM (SEM) figure explanation is homogeneous, in micron order.
Further, present invention also offers a kind of preparation method of described functional polymer microsphere, including following step
Suddenly：
(1) dispersant is added in three neck round bottom, stirring, and logical nitrogen deoxygenation is started after intensification；
(2) after being well mixed monomer, crosslinking agent and pore-foaming agent in beaker, add initiator fully to dissolve and be configured to list
Body phase；
(3) under conditions of stirring, the single phase in step (2) is dividedly in some parts into the dispersant in step (1) after deoxygenation
In, while carrying out logical nitrogen deoxygenation during being dividedly in some parts；Single phase carries out polymerisation after adding, and obtains polymeric beads
Grain；
(4) it is uncrosslinked to remove after first washing the polymer beads for obtaining with water 2～3 times, then with 3～5h of acetone extraction
Homopolymers, then at 40 DEG C be vacuum dried, obtain porous crosslinked polymeric bead；
(5) using the lactone modified porous crosslinked polymeric bead of propyl sulfonic acid, after modification terminates, filter and filter off propyl sulfonic acid
Lactone, deionized water and methyl alcohol are dried after respectively washing 3 times, finally prepare functional polymer microsphere.
In the present invention, it is preferred to, dispersant described in step (1) is water-soluble for the polyvinyl alcohol that volume fraction is 0.7%
Liquid, to be warming up to 69～71 DEG C, the speed of the stirring is 490～510rpm/min, the logical nitrogen deoxygenation for the intensification
Time is 15min.
In the present invention, it is preferred to, monomer described in step (2) includes monomer 1 and monomer 2, the monomer 1, the list
Body 2, the crosslinking agent are 1.5～2.5 with the volume ratio of the pore-foaming agent:5～7:3～5:3～5；The crosslinking agent with it is described
The volume mass ratio of initiator is 3～5:0.25～0.35g, i.e., per described in 0.25～0.35g of crosslinking agent correspondence described in 3～5mL
Initiator；The monomer 1 be acrylate monomer, the monomer 2 be propenoic acid dialkyl amido ethyl ester monomer, the crosslinking
Agent is esters of acrylic acid, and the pore-foaming agent is n-hexane, and the initiator is benzoyl peroxide.
In the present invention, it is further preferred that the acrylate monomer be methyl methacrylate, methyl acrylate,
Ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl acrylate, EMA, butyl methacrylate or
EHMA；The propenoic acid dialkyl amido ethyl ester monomer is acrylic acid dimethyl amido ethyl ester, propylene
Sour diethyl amido ethyl ester, acrylic acid diisooctyl amido ethyl ester, dimethylaminoethyl acrylate methyl base amido ethyl ester, methyl-prop
Olefin(e) acid diethyl amido ethyl ester or methacrylic acid diisooctyl amido ethyl ester；The esters of acrylic acid is triethylene glycol two
Methacrylate, glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyvinyl alcohol
Diacrylate or triethanolamine triacrylate；The body of the monomer 1, the monomer 2, the crosslinking agent and the pore-foaming agent
Product is than being 2:6:4:4；The crosslinking agent is 4 with the volume mass ratio of the initiator:0.30g, i.e., crosslinking agent pair described in per 4mL
Answer initiator described in 0.30g.
In the present invention, the monomer 1 is the acrylate monomer for removing polymerization inhibitor, and polymerization inhibitor is that a kind of industry is helped
Agent, is commonly used to prevent the carrying out of polymerization.Inhibition agent molecule and chain radical reaction, form non-free radical material or can not
The low activity free radical of initiation, so that polymerization.It is single in order to avoid monomer is polymerized during storage, transport etc.
A small amount of polymerization inhibitor is often added in body, is again being removed it using front.
In the present invention, it is preferred to, the speed stirred described in step (3) is 490～510rpm/min, described to add in batches
The time for entering is 30min, and the time of the logical nitrogen deoxygenation is 15min, and the polymerisation is the constant temperature at a temperature of 90 DEG C
3.5～4.5h of reaction, the dispersant is 100 with the volume ratio of the crosslinking agent:3～5.
In the present invention, it is further preferred that polymerisation is the isothermal reaction at a temperature of 90 DEG C described in step (3)
Cool down after 4h, terminate polymerisation；The dispersant is 100 with the volume ratio of the crosslinking agent:4.
In the present invention, the mixing speed in step (3) is identical with the mixing speed in step (1), good in order to ensure
Monomer dispersion, nitrogen deoxygenation 15min is led in this step.
In the present invention, it is preferred to, the lactone modified porous crosslinked polymeric bead of propyl sulfonic acid is adopted described in step (5)
Concretely comprise the following steps：By propyl sulfonic acid lactone and porous crosslinked polymeric bead according to mass ratio 1:1 is dissolved in methyl alcohol and tetrahydrochysene furan
In the mixed solution muttered, stir at 50 DEG C after 48h, filter and filter off propyl sulfonic acid lactone, deionized water and methyl alcohol are done after respectively washing 3 times
It is dry, finally prepare functional polymer microsphere；Methyl alcohol and the volume ratio of tetrahydrofuran are 1 in wherein described mixed solution:1,
The mixed solution is 25～35 with the volume mass ratio of the porous crosslinked polymeric bead:2.0～3.0, i.e., per 25～
Porous crosslinked polymeric bead described in 2.0～3.0g of mixed solution correspondence described in 35mL.
In the present invention, the distribution of surface-active site is obtained using the lactone modified porous crosslinked polymeric bead of propyl sulfonic acid
Uniform functional polymer microsphere.
In the present invention, it is further preferred that the volume matter of the mixed solution and the porous crosslinked polymeric bead
Amount is than being 30:2.5, i.e., porous crosslinked polymeric bead described in mixed solution correspondence 2.5g described in per 30mL.
The preparation method of the functional polymer microsphere of the present invention is mainly including the preparation and modification of cross-linked polymer.Preferably
Step is：To remove the EMA of polymerization inhibitor first in beaker, methacrylic acid diethyl amido ethyl ester,
After TEGDMA and n-hexane are well mixed, benzoyl peroxide (BPO) fully dissolving is added to be configured to
Single phase；Polyvinyl alcohol water solution is added in three neck round bottom, through heating up, stirring, after logical nitrogen deoxygenation, is kept stirring for
Speed, the single phase for preparing is dividedly in some parts in three neck round bottom, to ensure good monomer dispersion, leads to nitrogen deoxygenation,
Then about 4h is reacted at 90 DEG C, is terminated polymerisation and is removed uncrosslinked homopolymers, obtain cross linked porous after vacuum drying
Polymer globules；Finally porous crosslinked polymeric bead is mixed in into what 30mL equal-volumes mixed with the propyl sulfonic acid lactone of equivalent
In methyl alcohol and tetrahydrofuran solution, unreacted propyl sulfonic acid lactone is stirred and be filtered to remove, deionized water and first is respectively adopted
Functional polymer microsphere is dried to obtain after alcohol cleaning, it is stand-by.
Further, present invention also offers described functional polymer microsphere is in solid phase extraction column stuffing is prepared
Using.
In the present invention, it is preferred to, the solid phase extraction column stuffing be used for separation and concentration environment water present in copper,
Zinc, arsenic, cadmium, lead, mercury, tin, bismuth, vanadium, chromium, cobalt, antimony, the heavy metal species ion of barium 13.
Functional polymer microsphere obtained by the present invention is made into the core filler of solid-phase extraction column, then by SPE
Post is connected with high pressure pump, for the separation and concentration of heavy metal ion in environment water.Solid phase extraction method (SPE) is directed to one
As filler generally need to adjust pH value, target analysis species are few and the low shortcoming of separation and concentration efficiency, and by the work(of the present invention
Can polymer microballoon make the core filler of solid-phase extraction column, there is provided it is a kind of can under gentle neutrallty condition quick separating it is rich
The method of heavy metal ion in collection environment water.This method is without the need for any external agent, it is only necessary to 8min, can be achieved with copper, zinc,
Arsenic, cadmium, lead, mercury, tin, the quick adsorption of the heavy metal species ion of bismuth eight, adsorption rate obtains very high suction more than 92%
Attached efficiency.Simultaneously other heavy metal ion (vanadium, chromium, cobalt, antimony, barium) also can be reached with more than 50% adsorption efficiency.
Compared with prior art, the method for the present invention has the advantages that：
Functional polymer microsphere prepared by the present invention possesses draws materials extensively, and economic and environment-friendly, easily modification and adsorption efficiency are high
The features such as, compensate for the deficiency of presently commercially available SPE material；The core filler of solid phase extraction manipulations is used it for, can be simultaneously
The separation and concentration of 13 heavy metal species ions in environment water is realized, to copper, zinc, arsenic, cadmium, lead, mercury, tin, the heavy metal species of bismuth eight
The adsorption rate of ion is more than 92%, while can also reach more than 50% to other heavy metal ion (vanadium, chromium, cobalt, antimony, barium)
Adsorption efficiency；The present invention is simple to operation, and treatment effect is fast, and inorganic pollution separates analysis neck in actual environment water body
Domain has considerable application prospect.
Description of the drawings
Accompanying drawing is to combine specific process embodiment, specifically understands technique trend.
Fig. 1 is the infrared spectrogram of the functional polymer microsphere of the present invention；
Fig. 2 is the scanning electron microscope (SEM) photograph of the functional polymer microsphere of the present invention；
Fig. 3 is impact of the flow velocity to the heavy metal ion adsorbed effect of target；
Fig. 4 is impact of the sample volume to mesh heavy metal removal rate；
Fig. 5 is comparison diagram before and after eco material science SPE absorption.
Specific embodiment
To make the object, technical solutions and advantages of the present invention become more apparent, below in conjunction with specific embodiment, and reference
Accompanying drawing, the present invention is described in more detail.
The preparation of the functional polymer microsphere of embodiment 1
With EMA as monomer 1, methacrylic acid diethyl amido ethyl ester is monomer 2 and three to the present embodiment
Ethylene glycol dimethacrylate carries out the synthesis of functional polymer microsphere for crosslinking agent, and synthesis path is as follows：
Specifically include following steps：
(1) polyvinyl alcohol for adding 100mL volume fractions to be 0.7% in volume is for the three neck round-bottomed bottles of 250mL is water-soluble
Liquid is dispersant, is warming up to 69～71 DEG C, starts stirring, and mixing speed is 490～510rpm/min, leads to nitrogen deoxygenation 15min；
(2) the 2mL EMAs (monomer 1) of polymerization inhibitor, 6mL methacrylic acids will be removed in 50mL beakers
Diethyl amido ethyl ester (monomer 2), 4mL TEGDMAs (crosslinking agent) and 4mL n-hexanes (pore-foaming agent)
After being well mixed, 0.30g benzoyl peroxides (BPO) (initiator) fully dissolving is added to be configured to single phase；
(3) speed is kept stirring for, mixing speed is 490～510rpm/min, and the single phase for preparing is divided in 30min
Criticize and add in three neck round bottom, to ensure good monomer dispersion, lead to nitrogen deoxygenation 15min；Continue after adding in 90 DEG C of perseverances
Cool down after temperature reaction 4h, terminate polymerisation, obtain polymer beads；
(4) after first washing the polymer beads of gained with water 2～3 times, 3～5h of acetone extraction is used in Soxhlet extractor,
To remove uncrosslinked homopolymers, then it is vacuum dried at 40 DEG C, obtains porous crosslinked polymeric bead；
(5) 2.5g porous crosslinked polymerics bead is mixed in into what 30mL equal-volumes mixed with the propyl sulfonic acid lactone of equivalent
In methyl alcohol and tetrahydrofuran solution, after 50 DEG C of stirring 48h, filter and filter off propyl sulfonic acid lactone, deionized water and methyl alcohol respectively wash 3 times
After be dried, finally prepare functional polymer microsphere.
The preparation of the functional polymer microsphere of embodiment 2
With EMA as monomer 1, methacrylic acid diethyl amido ethyl ester is monomer 2 and three to the present embodiment
Ethylene glycol dimethacrylate carries out the synthesis of functional polymer microsphere for crosslinking agent.
Specifically include following steps：
(1) polyvinyl alcohol for adding 100mL volume fractions to be 0.7% in volume is for the three neck round-bottomed bottles of 250mL is water-soluble
Liquid is dispersant, is warming up to 69～71 DEG C, starts stirring, and mixing speed is 490～510rpm/min, leads to nitrogen deoxygenation 15min；
(2) the 1.5mL EMAs (monomer 1) of polymerization inhibitor, 5mL metering systems will be removed in 50mL beakers
Sour diethyl amido ethyl ester (monomer 2), 3mL TEGDMAs (crosslinking agent) and 3mL n-hexane (pores
Agent) be well mixed after, add 0.25g benzoyl peroxides (BPO) (initiator) fully dissolving to be configured to single phase；
(3) speed is kept stirring for, mixing speed is 490～510rpm/min, and the single phase for preparing is divided in 30min
Criticize and add in three neck round bottom, to ensure good monomer dispersion, lead to nitrogen deoxygenation 15min；Continue after adding in 90 DEG C of perseverances
Cool down after temperature reaction 3.5h, terminate polymerisation, obtain polymer beads；
(4) after first washing the polymer beads of gained with water 2～3 times, 3～5h of acetone extraction is used in Soxhlet extractor,
To remove uncrosslinked homopolymers, then it is vacuum dried at 40 DEG C, obtains porous crosslinked polymeric bead；
(5) 2.0g porous crosslinked polymerics bead is mixed in into what 25mL equal-volumes mixed with the propyl sulfonic acid lactone of equivalent
In methyl alcohol and tetrahydrofuran solution, after 50 DEG C of stirring 48h, filter and filter off propyl sulfonic acid lactone, deionized water and methyl alcohol respectively wash 3 times
After be dried, finally prepare functional polymer microsphere.
The preparation of the functional polymer microsphere of embodiment 3
With EMA as monomer 1, methacrylic acid diethyl amido ethyl ester is monomer 2 and three to the present embodiment
Ethylene glycol dimethacrylate carries out the synthesis of functional polymer microsphere for crosslinking agent.
Specifically include following steps：
(1) polyvinyl alcohol for adding 100mL volume fractions to be 0.7% in volume is for the three neck round-bottomed bottles of 250mL is water-soluble
Liquid is dispersant, is warming up to 69～71 DEG C, starts stirring, and mixing speed is 490～510rpm/min, leads to nitrogen deoxygenation 15min；
(2) the 2.5mL EMAs (monomer 1) of polymerization inhibitor, 7mL metering systems will be removed in 50mL beakers
Sour diethyl amido ethyl ester (monomer 2), 5mL TEGDMAs (crosslinking agent) and 5mL n-hexane (pores
Agent) be well mixed after, add 0.35g benzoyl peroxides (BPO) (initiator) fully dissolving to be configured to single phase；
(3) speed is kept stirring for, mixing speed is 490～510rpm/min, and the single phase for preparing is divided in 30min
Criticize and add in three neck round bottom, to ensure good monomer dispersion, lead to nitrogen deoxygenation 15min；Continue after adding in 90 DEG C of perseverances
Cool down after temperature reaction 4.5h, terminate polymerisation, obtain polymer beads；
(4) after first washing the polymer beads of gained with water 2～3 times, 3～5h of acetone extraction is used in Soxhlet extractor,
To remove uncrosslinked homopolymers, then it is vacuum dried at 40 DEG C, obtains porous crosslinked polymeric bead；
(5) 3.0g porous crosslinked polymerics bead is mixed in into what 35mL equal-volumes mixed with the propyl sulfonic acid lactone of equivalent
In methyl alcohol and tetrahydrofuran solution, after 50 DEG C of stirring 48h, filter and filter off propyl sulfonic acid lactone, deionized water and methyl alcohol respectively wash 3 times
After be dried, finally prepare functional polymer microsphere.
The preparation of the functional polymer microsphere of embodiment 4
With ethyl acrylate as monomer 1, acrylic acid dimethyl amido ethyl ester is monomer 2 and polyvinyl alcohol two to the present embodiment
Acrylate carries out the synthesis of functional polymer microsphere for crosslinking agent.
Specifically include following steps：
(1) polyvinyl alcohol for adding 100mL volume fractions to be 0.7% in volume is for the three neck round-bottomed bottles of 250mL is water-soluble
Liquid is dispersant, is warming up to 69～71 DEG C, starts stirring, and mixing speed is 490～510rpm/min, leads to nitrogen deoxygenation 15min；
(2) the 2mL ethyl acrylates (monomer 1) of polymerization inhibitor, 6mL acrylic acid dimethyl amines will be removed in 50mL beakers
After base ethyl ester (monomer 2), 4mL polyvinyl alcohol diacrylates (crosslinking agent) and 4mL n-hexanes (pore-foaming agent) are well mixed, plus
Enter 0.30g benzoyl peroxides (BPO) (initiator) fully dissolving and be configured to single phase；
(3) speed is kept stirring for, mixing speed is 490～510rpm/min, and the single phase for preparing is divided in 30min
Criticize and add in three neck round bottom, to ensure good monomer dispersion, lead to nitrogen deoxygenation 15min；Continue after adding in 90 DEG C of perseverances
Cool down after temperature reaction 4h, terminate polymerisation, obtain polymer beads；
(4) after first washing the polymer beads of gained with water 2～3 times, 3～5h of acetone extraction is used in Soxhlet extractor,
To remove uncrosslinked homopolymers, then it is vacuum dried at 40 DEG C, obtains porous crosslinked polymeric bead；
(5) 2.5g porous crosslinked polymerics bead is mixed in into what 30mL equal-volumes mixed with the propyl sulfonic acid lactone of equivalent
In methyl alcohol and tetrahydrofuran solution, after 50 DEG C of stirring 48h, filter and filter off propyl sulfonic acid lactone, deionized water and methyl alcohol respectively wash 3 times
After be dried, finally prepare functional polymer microsphere.
The preparation of the functional polymer microsphere of embodiment 5
With Isooctyl acrylate monomer as monomer 1, methacrylic acid diisooctyl amido ethyl ester is monomer 2 and second to the present embodiment
Omega-diol diacrylate carries out the synthesis of functional polymer microsphere for crosslinking agent.
Specifically include following steps：
(1) polyvinyl alcohol for adding 100mL volume fractions to be 0.7% in volume is for the three neck round-bottomed bottles of 250mL is water-soluble
Liquid is dispersant, is warming up to 69～71 DEG C, starts stirring, and mixing speed is 490～510rpm/min, leads to nitrogen deoxygenation 15min；
(2) the 1.5mL Isooctyl acrylate monomers (monomer 1) of polymerization inhibitor, 5mL methacrylic acids will be removed in 50mL beakers
Diisooctyl amido ethyl ester (monomer 2), 3mL glycol diacrylates (crosslinking agent) and 3mL n-hexanes (pore-foaming agent) mix
After uniform, 0.25g benzoyl peroxides (BPO) (initiator) fully dissolving is added to be configured to single phase；
(3) speed is kept stirring for, mixing speed is 490～510rpm/min, and the single phase for preparing is divided in 30min
Criticize and add in three neck round bottom, to ensure good monomer dispersion, lead to nitrogen deoxygenation 15min；Continue after adding in 90 DEG C of perseverances
Cool down after temperature reaction 3.5h, terminate polymerisation, obtain polymer beads；
(4) after first washing the polymer beads of gained with water 2～3 times, 3～5h of acetone extraction is used in Soxhlet extractor,
To remove uncrosslinked homopolymers, then it is vacuum dried at 40 DEG C, obtains porous crosslinked polymeric bead；
(5) 2.0g porous crosslinked polymerics bead is mixed in into what 25mL equal-volumes mixed with the propyl sulfonic acid lactone of equivalent
In methyl alcohol and tetrahydrofuran solution, after 50 DEG C of stirring 48h, filter and filter off propyl sulfonic acid lactone, deionized water and methyl alcohol respectively wash 3 times
After be dried, finally prepare functional polymer microsphere.
The preparation of the functional polymer microsphere of embodiment 6
With methyl methacrylate as monomer 1, acrylic acid diisooctyl amido ethyl ester is the second of monomer 2 and three to the present embodiment
Hydramine triacrylate carries out the synthesis of functional polymer microsphere for crosslinking agent.
Specifically include following steps：
(1) polyvinyl alcohol for adding 100mL volume fractions to be 0.7% in volume is for the three neck round-bottomed bottles of 250mL is water-soluble
Liquid is dispersant, is warming up to 69～71 DEG C, starts stirring, and mixing speed is 490～510rpm/min, leads to nitrogen deoxygenation 15min；
(2) the 2.5mL methyl methacrylates (monomer 1) of polymerization inhibitor, 7mL acrylic acid two will be removed in 50mL beakers
Iso-octyl amido ethyl ester (monomer 2), 5mL triethanolamine triacrylates (crosslinking agent) and 5mL n-hexanes (pore-foaming agent) mix
After uniform, 0.35g benzoyl peroxides (BPO) (initiator) fully dissolving is added to be configured to single phase；
(3) speed is kept stirring for, mixing speed is 490～510rpm/min, and the single phase for preparing is divided in 30min
Criticize and add in three neck round bottom, to ensure good monomer dispersion, lead to nitrogen deoxygenation 15min；Continue after adding in 90 DEG C of perseverances
Cool down after temperature reaction 4.5h, terminate polymerisation, obtain polymer beads；
(4) after first washing the polymer beads of gained with water 2～3 times, 3～5h of acetone extraction is used in Soxhlet extractor,
To remove uncrosslinked homopolymers, then it is vacuum dried at 40 DEG C, obtains porous crosslinked polymeric bead；
(5) 3.0g porous crosslinked polymerics bead is mixed in into what 35mL equal-volumes mixed with the propyl sulfonic acid lactone of equivalent
In methyl alcohol and tetrahydrofuran solution, after 50 DEG C of stirring 48h, filter and filter off propyl sulfonic acid lactone, deionized water and methyl alcohol respectively wash 3 times
After be dried, finally prepare functional polymer microsphere.
The functional polymer microsphere prepared to embodiment 1-6 carries out analysis of physical and chemical property, and using densitometer it is determined
Density is 0.98.C is measured using elemental analyser, H, N, O percentage composition is respectively C：46.64%, H：7.93%, N：
1.66%, O：39.3%；Inductively-coupled plasma spectrometer is adopted to measure S contents for 1.75%.
Structure and pattern table are carried out to functional polymer microsphere using Fourier infrared spectrograph and ESEM (SEM)
Levy, infrared spectrum and SEM patterns are shown in respectively Fig. 1 and Fig. 2.It will be seen from figure 1 that 530cm-1,620cm-1,1068cm-1With
1190cm-1Locate as sulfonic characteristic absorption peak, and 1730cm-1Place then absorbs for the C=O stretching vibrations of methacrylate
Peak；The prepared functional polymer microsphere particle diameter distribution of Fig. 2 explanations is homogeneous, in micron order.
Separation and concentration of the functional polymer microsphere of test example 1 as solid phase extraction column stuffing heavy metal ion standard items
The foundation and checking of 1.1 solid phase extraction methods
Comprise the following steps that：
1) functional polymer microsphere that 430mg embodiments 1 are prepared is weighed, specification is uniformly added into for 50 × 4.6mm's
In stainless steel sky chromatographic column, SPE enriching columns are made by oneself.SPE enriching columns are connected with STI type high pressure pumps using PEEK pipes.
Under 1mL/min flow velocitys, 5% methanol solution and pure water cleaning enriching column are respectively adopted, are rinsed to high-pressure pump pressure stability.
2) a series of concentration are prepared and is respectively 0.2ng/mL, 0.5ng/mL, 1.0ng/mL, 2.0ng/mL, 5.0ng/mL's
Copper, zinc, arsenic, cadmium, lead, mercury, tin, bismuth mixed standard solution.
3) it is that in the range of 1～7mL/min, the flow velocity of investigation high pressure pump is to the heavy metal ion adsorbed effect of target in flow velocity
The impact of rate.From figure 3, it can be seen that as flow velocity increases to 5mL/min, adsorption efficiency has no significant change, but when stream
When speed continues to increase, the rate of recovery begins to decline.Its reason is probably that too high flow velocity can cause object and enriching column active sites
Between point caused by contact not exclusively.
4) it is 10mL to prepare a series of volumes, and the mixed standard solution of 20mL, 30mL, 40mL, 50mL and 60mL investigates sample
Impact of the product volume to target heavy metal removal rate, as shown in Figure 4.When loading volume is higher than 40mL, the rate of recovery starts
Decline, its reason is possibly due to caused by enriching column adsorption capacity saturation.
6) by experimental condition optimization, under 5mL/min flow velocitys, above-mentioned mixed standard solution of the volume for 40mL is carried out
On-line solid phase extraction is operated, after the completion of sample adsorption, using 2%HNO3Eluant solution object.For each concentration gradient is entered
Three parallel absorb-elute operations of row, and band flow process is blank.
7) detected using icp mses (ICPMS), respectively to the huge sum of money before and after SPE absorption
Category Ar ion mixing solution carries out assay, compares concentration before and after absorption, calculates adsorption efficiency.
8) while being measured to the object ion in eluent, adsorption efficiency and enrichment factor are calculated.
The method of above-mentioned foundation is investigated to the adsorption effect of the heavy metal ion mixed standard solution of variable concentrations gradient and
Elution efficiency.As a result show, for variable concentrations gradient heavy metal ion mixed standard solution (copper, zinc, arsenic, cadmium, lead, mercury,
Tin, bismuth), can realize more than 92% adsorption effect and elution efficiency, while to the heavy metal of other variable concentrations gradients from
Sub- mixed standard solution (vanadium, chromium, cobalt, antimony, barium) can also reach more than 50% adsorption efficiency.
Solid phase extraction method (SPE) generally needs to adjust pH value for general filler, and target analysis species are few and separate
The low shortcoming of bioaccumulation efficiency, and the functional polymer microsphere of the present invention is made into the core filler of solid-phase extraction column, there is provided one
Kind can in fast separating concentration environment water under gentle neutrallty condition heavy metal ion method.This method is without the need for any outer
Carry out reagent, it is only necessary to 8min, can be achieved with the quick adsorption of heavy metal ion that may be present in environment water.
The separation and concentration of 1.2 above-mentioned solid phase extracting process heavy metal ionic environment standard items
By eco material science GSBZ50009-88 (Copper in Water, lead, zinc, cadmium) and GSB07-3171-2014 (water quality arsenic)
As analysis object, the feasibility and accuracy of verification method.Because the initial concentration of object in standard sample is higher, divide
It is other that they are carried out to carry out SPE again after 200 times and 20 times dilutions, while carrying out blank and Duplicate Samples analysis.ICP-
MS detections adopt KED analytical models to improve signal-to-background ratio.When helium gas flow is 4.091mL/min, can effectively eliminate double
The impact of electric charge interfering ion, background signal is significantly reduced.Under the experiment condition of optimization, i.e., under 5mL/min flow velocitys, to body
Product carries out on-line solid phase extraction operation for the above-mentioned mixed standard solution of 40mL, after the completion of sample adsorption, using 2%HNO3Solution
Wash-out object.For each concentration gradient carries out three parallel absorb-elute operations, and band flow process is blank, for environment mark
5 heavy metal species ions in quasi- sample, can realize more than 92% adsorption efficiency, as shown in Figure 5.
Separation and concentration of the functional polymer microsphere of test example 2 as solid phase extraction column stuffing to environment water body example
Lake water and river pick up from respectively Fujian Province and Zhejiang inside the province, and the principle of multidraw is followed in sampling process, to protect
Card samples' representativeness and homogeneity.First big algae and particulate matter are removed with screen pack in gatherer process, after acidifying immediately
Deliver to laboratory to be analyzed (preserved with ice bag during transport).Before sample on-line preconcentration, first passing around aperture is
0.22 μm of cellulose acetate sheets are filtered, and are then transferred in clean brown bottle.For volume is the environmental water sample of 40mL,
Under 5mL/min pump speeds, to each sample parallel analysis 3 times, while 3 flow process blank samples of band.Detected using ICP-MS devices,
The change of concentration, calculates the adsorption efficiency of every kind of heavy metal ion before and after contrast Solid phase extraction separation enrichment, more than 92%,
Obtain gratifying separation and concentration effect.Finally, tested to prepared polymeric material and solid phase using recovery of standard addition
Extracting process is verified.As a result show, the adsorption rate of copper, zinc, arsenic, cadmium, lead, mercury, tin, the heavy metal species ion of bismuth eight is existed
More than 92%, while can also reach more than 50% adsorption efficiency to vanadium, chromium, cobalt, antimony, the heavy metal species ion of barium five.
In sum, the functional polymer microsphere prepared by the present invention possesses and draws materials extensively, economic and environment-friendly, easily modification and suction
The features such as attached efficiency high, compensate for the deficiency of presently commercially available SPE material；The core for using it for solid phase extraction manipulations is filled out
Material, can simultaneously realize the separation and concentration of 13 heavy metal species ions in environment water, to copper, zinc, arsenic, cadmium, lead, mercury, tin, bismuth eight
The adsorption rate of heavy metal species ion is more than 92%, while also can reach to other heavy metal ion (vanadium, chromium, cobalt, antimony, barium)
More than 50% adsorption efficiency；The present invention is simple to operation, and treatment effect is fast, the inorganic pollution point in actual environment water body
There is considerable application prospect from analysis field.
Those of ordinary skill in the art should be understood：The discussion of any of the above embodiment is exemplary only, not
It is intended to imply that the scope of the present disclosure (including claim) is limited to these examples；Under the thinking of the present invention, above example
Or can also be combined between the technical characteristic in different embodiments, and there is the different aspect of the present invention as above
Many other changes, in order to it is simple and clear they provide without in details.Therefore, it is all within the spirit and principles in the present invention,
Any omission, modification, equivalent, improvement for being made etc., should be included within the scope of the present invention.
Claims (10)
1. a kind of functional polymer microsphere, it is characterised in that the mass percent of each element is as follows in the polymer microballoon：C:
46.64%, H:7.93%, N:1.66%, O:39.3%, S:1.75%；The structural formula of the polymer microballoon such as formula (I) institute
Show：
2. a kind of preparation method of functional polymer microsphere according to claim 1, it is characterised in that including following step
Suddenly：
(1) dispersant is added in three neck round bottom, stirring, and logical nitrogen deoxygenation is started after intensification；
(2) after being well mixed monomer, crosslinking agent and pore-foaming agent in beaker, add initiator fully to dissolve and be configured to monomer
Phase；
(3) under conditions of stirring, the single phase in step (2) is dividedly in some parts in the dispersant in step (1) after deoxygenation,
While carrying out logical nitrogen deoxygenation during being dividedly in some parts；Single phase carries out polymerisation after adding, and obtains polymer beads；
(4) it is uncrosslinked equal to remove after first washing the polymer beads for obtaining with water 2～3 times, then with 3～5h of acetone extraction
Polymers, is then vacuum dried at 40 DEG C, obtains porous crosslinked polymeric bead；
(5) using the lactone modified porous crosslinked polymeric bead of propyl sulfonic acid, after modification terminates, filter and filter off in propyl sulfonic acid
Ester, deionized water and methyl alcohol are dried after respectively washing 3 times, finally prepare functional polymer microsphere.
3. the preparation method of functional polymer microsphere according to claim 2, it is characterised in that described in step (1) point
Powder is the polyvinyl alcohol water solution that volume fraction is 0.7%, and the intensification is to be warming up to 69～71 DEG C, the speed of the stirring
For 490～510rpm/min, the time of the logical nitrogen deoxygenation is 15min.
4. the preparation method of functional polymer microsphere according to claim 2, it is characterised in that single described in step (2)
Body includes monomer 1 and monomer 2, the monomer 1, the monomer 2, the crosslinking agent and the volume ratio of the pore-foaming agent be 1.5～
2.5:5～7:3～5:3～5；The crosslinking agent is 3～5 with the volume mass ratio of the initiator:0.25～0.35g, i.e., per 3
Initiator described in 0.25～0.35g of crosslinking agent correspondence described in～5mL；The monomer 1 is acrylate monomer, and the monomer 2 is
Propenoic acid dialkyl amido ethyl ester monomer, the crosslinking agent be esters of acrylic acid, the pore-foaming agent be n-hexane, the initiation
Agent is benzoyl peroxide.
5. the preparation method of functional polymer microsphere according to claim 4, it is characterised in that the acrylate monomer
For methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl acrylate, first
Base ethyl acrylate, butyl methacrylate or EHMA；The propenoic acid dialkyl amido ethyl ester monomer
For acrylic acid dimethyl amido ethyl ester, acrylic acid diethyl amido ethyl ester, acrylic acid diisooctyl amido ethyl ester, methyl
Acrylic acid dimethyl amido ethyl ester, methacrylic acid diethyl amido ethyl ester or methacrylic acid diisooctyl amido ethyl
Ester；The esters of acrylic acid is TEGDMA, glycol diacrylate, diethylene glycol diacrylate
Ester, triethylene glycol diacrylate, polyvinyl alcohol diacrylate or triethanolamine triacrylate；The monomer 1, the list
Body 2, the crosslinking agent are 2 with the volume ratio of the pore-foaming agent:6:4:4；The volume mass of the crosslinking agent and the initiator
Than for 4:0.30g, i.e., initiator described in crosslinking agent correspondence 0.30g described in per 4mL.
6. the preparation method of functional polymer microsphere according to claim 2, it is characterised in that step is stirred described in (3)
The speed mixed is 490～510rpm/min, and the time being dividedly in some parts is 30min, and the time of the logical nitrogen deoxygenation is
15min, the polymerisation is 3.5～4.5h of isothermal reaction at a temperature of 90 DEG C, the dispersant and the crosslinking agent
Volume ratio is 100:3～5.
7. the preparation method of functional polymer microsphere according to claim 2, it is characterised in that step is adopted described in (5)
With concretely comprising the following steps for the lactone modified porous crosslinked polymeric bead of propyl sulfonic acid：Propyl sulfonic acid lactone is polymerized with cross linked porous
Thing bead is according to mass ratio 1:1 is dissolved in the mixed solution of methyl alcohol and tetrahydrofuran, stirs at 50 DEG C after 48h, filters and filters off third
Base sultones, deionized water and methyl alcohol are dried after respectively washing 3 times, finally prepare functional polymer microsphere；It is wherein described mixed
It is 1 to close methyl alcohol and the volume ratio of tetrahydrofuran in solution:1, the body of the mixed solution and the porous crosslinked polymeric bead
Product mass ratio is 25～35:2.0～3.0, i.e., per cross linked porous poly- described in 2.0～3.0g of mixed solution correspondence described in 25～35mL
Compound bead.
8. the preparation method of functional polymer microsphere according to claim 7, it is characterised in that the mixed solution and institute
The volume mass ratio for stating porous crosslinked polymeric bead is 30:2.5, i.e., porous described in mixed solution correspondence 2.5g described in per 30mL
Globules of cross-linked polymers.
9. application of the functional polymer microsphere described in claim 1 in solid phase extraction column stuffing is prepared.
10. application of the functional polymer microsphere according to claim 9 in solid phase extraction column stuffing is prepared, its feature exists
In, the solid phase extraction column stuffing be used for copper present in separation and concentration environment water, zinc, arsenic, cadmium, lead, mercury, tin, bismuth, vanadium,
Chromium, cobalt, antimony, the heavy metal species ion of barium 13.
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