CN105037664A - Superparamagnetic advanced functional polymer monodisperse microspheres prepared by adopting swelling copolymerization method - Google Patents
Superparamagnetic advanced functional polymer monodisperse microspheres prepared by adopting swelling copolymerization method Download PDFInfo
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- CN105037664A CN105037664A CN201510412085.9A CN201510412085A CN105037664A CN 105037664 A CN105037664 A CN 105037664A CN 201510412085 A CN201510412085 A CN 201510412085A CN 105037664 A CN105037664 A CN 105037664A
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Abstract
The invention discloses superparamagnetic advanced functional polymer monodisperse microspheres prepared by adopting a swelling copolymerization method. The method comprises: firstly modifying the surfaces of ferroferric oxide nano microspheres (Fe3O4@SiO2) wrapped by silicon dioxide (SiO2) by using a double-bond group containing silane reagent to obtain a monodisperse microsphere product; and then, by taking the product as a seed, introducing styrene monomers and other ethylene comonomers in a swelling polymerization process to prepare corresponding polymerized microspheres. As the used initial raw material Fe3O4@SiO2 is superparamagnetic, the microspheres are endowed with a good superparamagnetic characteristic. The superparamagnetic copolymerized microspheres can be applied to adsorbing various compounds, particularly extracting, enriching and purifying trace compounds. As the monodisperse microspheres are magnetic, great convenience is brought when the monodisperse microspheres and mother liquor are separated after target compounds are absorbed. The product which serves as an adsorbent can be applied to multiple fields of pesticide residue detection, drug residue detection, human body trace biomass detection and the like. The magnetic copolymerized microspheres prepared by the method are uniform in shape and stable in performance.
Description
Technical field
The invention belongs to polymer chemistry field, Solid-Phase Extraction (SPE), Magnetic solid phases extraction (MSPE) and Analysis of Organic Substances technical field, be specially and relate to a kind of seed swelling legal system for superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon.
Background technology
The Solid-Phase Extraction material of vinyl pyrrolidone and styrene monomer copolymerization gained, owing to having hydrophilic radical and hydrophobic group simultaneously, to all kinds of polarity, non-polar compound, all there is favourable absorption effect, the more common C18 bonded silica gel of its adsorptive power is excellent, in the middle of the concentration and separation that can be widely used in various compound.But the concentration and separation work of the material for some denier, fiber material, with the separation operational difficulty sometimes of enrichment system, easily causes target separate substance to be lost.
Magnetic particle is in the concentration and separation of micro substance, because it has paramagnetic feature, after realization is to target substance enrichment, under the effect of externally-applied magnetic field, can be realized it easily with the separation between mother liquor, thus simplify or solve the difficult problem of fiber material with mother liquor separation for adsorbed target thing.
The two combines by the present invention, forms copolymerization, synthesized a kind of Premium Features polymkeric substance mono-dispersion microballoon having superparamagnetism, skeleton symbol: Fe with the magnetic microsphere in advance through double bond modified with " styrene monomer " and other " vinyl comonomer "
3o
4pLS.Products therefrom uniform particle sizes, form and performance are easy to control.The absorption to predetermined substance can well be applied to, retain to greatest extent target isolate especially micro substance enrichment be separated in the middle of.
Summary of the invention
The present invention seeks to the difficult problem that the fiber material in order to solve existing adsorbed target thing is separated with mother liquor, realize the absorption to predetermined substance, retain to greatest extent target isolate especially micro substance enrichment be separated, a kind of Premium Features polymkeric substance mono-dispersion microballoon having superparamagnetism is provided.
To achieve these goals, the present invention is by the following technical solutions: a kind of superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon adopting swelling copolymerization method to prepare is that the method by comprising the following steps is prepared and obtains:
(1) preparation of single dispersing seed microballoon: surface has been wrapped up the ferriferrous oxide nano magnetic ball Fe after silicon-dioxide
3o
4siO
2join in the mixed system of second alcohol and water, add a small amount of triethylamine, under nitrogen protection, add the silane reagent containing double bond group, be heated to silane reagent hydrolysis temperature, to silane reagent and SiO
2layer silicone hydroxyl condensation reaction is complete, is separated by single dispersing seed microballoon under additional the action of a magnetic field with system, uses water and washing with alcohol, drying respectively;
(2) seed swelling copolymerization:
I, the single dispersing seed microballoon of preparation is suspended in the aqueous solution containing tensio-active agent and stablizer, adds a small amount of non-proton organic solvent, nitrogen deoxygenation, rapid stirring even for some time, form stable emulsion A; II, monomer, comonomer and non-proton organic solvent are mixed, slowly join in latex A under nitrogen protection, stirring is carried out fully swelling, forms emulsion B;
III, after adding initiator in emulsion B, system is heated to polymerization temperature and is polymerized to and reacts completely, after having reacted, under additional the action of a magnetic field, by product separation, with dehydrated alcohol and acetone supersound washing repeatedly, low-temperature vacuum drying obtains product.
The described silane reagent containing double bond group is methacrylic acid-3-(trimethoxysilyl) propyl ester or vinyltrimethoxy silane; Described monomer is the hydrocarbon monomer that side chain contains phenyl ring, is specially vinylbenzene, divinylbenzene etc.; Comonomer is N-V-Pyrol RC, acrylate or methyl methacrylate etc.
Described stablizer is water-soluble cellulose ether, Polyvinylpyrolidone (PVP) or Vltra tears; Tensio-active agent is negatively charged ion, positively charged ion or nonionic surface active agent etc.; Described non-protonic solvent is toluene, normal heptane, normal hexane or whiteruss etc.
Described initiator position benzoyl peroxide, t-butyl per(oxy)benzoate or Diisopropyl azodicarboxylate etc.
Described Fe
3o
4siO
2particle diameter be 50nm ~ 2 μm.
In described step (1), the hydrolysis temperature of silane reagent is 50 ~ 80 DEG C.
Condensation reaction time in described step (1) is 4 ~ 12 hours.
In described step (2) the Ith step, the weight percent of seed microballoon, tensio-active agent, stablizer, water, non-proton organic solvent is: (1.2 ~ 1.8): (4 ~ 6): (0.8 ~ 1.2): (560 ~ 840): (8 ~ 12); In IIth step and III, the weight percent of monomer, comonomer, non-proton organic solvent and initiator is: (4.5 ~ 7.5): (4 ~ 6): (7 ~ 11): (0.1 ~ 1.5).
In described step (2) the Ith step, churning time is 3 ~ 20 hours, and the emulsion made is not stratified.
Stirring the swelling time in described step (2) the IIth step is 2 ~ 12 hours, and the emulsion made is not stratified.
The present invention has prepared a kind of superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon (skeleton symbol: Fe by establishing one " swelling copolymerization method "
3o
4pLS).Gained magnetic polymer mono-dispersion microballoon uniform particle sizes, present single dispersing, to polarity and apolar substance, all there is good adsorption effect, and have superparamagnetism due to microballoon, under the effect of externally-applied magnetic field, can be convenient realize its separation with enrichment mother liquor.
This magnetic copolymerization microsphere can be applied to the various compound of absorption, especially for the extraction of minor compound, enrichment and purification.Because himself band is magnetic, after having adsorbed target compound, bring considerable ease with during mother liquor lock out operation.This product can be used as that sorbent material is applied in the residual detection of agriculture, drug residue detects, multiple field such as micro-biological substance detection in human body.The form of magnetic copolymerization microsphere prepared by the method is homogeneous, stable performance.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of embodiment.
Fig. 2 is starting raw material Fe in embodiment
3o
4siO
2scanning electron microscope phenogram.
Fig. 3 prepares seed microballoon Fe in embodiment
3o
4the scanning electron microscope phenogram of MPS.
Fig. 4 is copolymerized product Fe in embodiment
3o
4the scanning electron microscope phenogram of PLS.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples only for illustration of the present invention but not for limiting scope of the present invention.
Fig. 1 is preparation technology's schema of the superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon adopting swelling copolymerization method to prepare.
(1) single dispersing seed microballoon Fe
3o
4the preparation of MPS:
375mL dehydrated alcohol, 125mL water and 3gFe is added in 1000mL there-necked flask
3o
4siO
2, stir.Nitrogen protection, adds 8mL ammoniacal liquor, after stirring, drips the mixing solutions of 10mL dehydrated alcohol and 8mLMPS in system, drips after finishing completely and is warming up to 60 DEG C, continues stirring reaction and spends the night.By the Fe of preparation
3o
4after MPS is separated by externally-applied magnetic field, successively by washed with de-ionized water four times remove ammoniacal liquor and salt impurity, then to clarify to liquid phase for five times with ethanol purge, after product separation being gone out with magnet, dry must product.
(2) Fe is prepared in seed swelling copolymerization
3o
4pLS:
To in 2000mL there-necked flask, add 700mL deionized water, pass into nitrogen deoxygenation 30 minutes.Add single dispersing seed microballoon Fe prepared in 1.5g step 1
3o
4mPS, 5g sodium laurylsulfonate, 1g Vltra tears and 10mL toluene, continue to be stirred to system and be uniformly dispersed, obtain stable emulsion A, latex A is not stratified.
Under nitrogen protection, 6.1mL divinylbenzene, 5.1mLN-vinyl pyrrolidone and 10mL toluene are mixed, joins under high-speed stirring in latex A, finish and continue high-speed stirring for some time, system is uniformly dispersed, not stratified, obtain emulsion B.
In emulsion B, add 0.1g Diisopropyl azodicarboxylate, then system is warming up to 75 ~ 80 DEG C, under continuing nitrogen protection, insulation reaction is spent the night.Next day, be down to room temperature, under externally-applied magnetic field, by product separation, with dehydrated alcohol and acetone repetitive scrubbing, the product of room temperature in vacuo drying.
(3) material characterizes:
1. scanning electron microscope collection of illustrative plates
Utilize Electronic Speculum respectively to the raw materials used Fe of preparation superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon
3o
4siO
2, prepared seed microballoon Fe
3o
4mPS and the finished product Fe
3o
4pLS characterizes.Fig. 2 is starting raw material Fe
3o
4siO
2scanning electron microscope phenogram, synthesized voluntarily by our company; Fig. 3 is prepared seed microballoon Fe
3o
4the scanning electron microscope phenogram of MPS; Fig. 4 is the finished product Fe
3o
4the scanning electron microscope phenogram of PLS.Can find out that the median size of three is all at about 500nm from Fig. 2, Fig. 3 and Fig. 4, and present monodisperse spheres.But the apparent form that scanning electron microscope shows Fig. 2, Fig. 3 and Fig. 4 there occurs considerable change, show the coated success of Targeting groups.
2. Fe
3o
4pLS application example
With the superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon Fe prepared by step (2)
3o
4pLS has carried out enriching and recovering experiment to agricultural chemicals " Chlorpyrifos 94 ", examines the rate of recovery, and has carried out the rate of recovery compare with certain commercially available SPE pillar recovering effect.
Be in " Chlorpyrifos 94 " water sample of 50ppb to 10mL concentration, accurately add 50mgFe
3o
4pLS microballoon, stirs.Externally-applied magnetic field adsorbs, and after removing supernatant liquor, add the meoh eluate of 5ml, externally-applied magnetic field adsorbs, and removes Fe
3o
4pLS microballoon, detects gained elutriant.Experimental result shows, Fe
3o
4the enriching and recovering rate of PLS microballoon to " Chlorpyrifos 94 " water sample is 71.32%, and the enriching and recovering rate of commercially available SPE pillar is only 21.34%.Fe
3o
4the enriching and recovering effect of PLS microballoon is better than SPE pillar.
Claims (10)
1. adopt the superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon prepared of swelling copolymerization method, it is characterized in that method preparation by comprising the following steps and obtain:
(1) preparation of single dispersing seed microballoon: surface has been wrapped up the ferriferrous oxide nano magnetic ball Fe after silicon-dioxide
3o
4siO
2join in the mixed system of second alcohol and water, add a small amount of triethylamine, under nitrogen protection, add the silane reagent containing double bond group, be heated to silane reagent hydrolysis temperature, to silane reagent and SiO
2layer silicone hydroxyl condensation reaction is complete, is separated by single dispersing seed microballoon under additional the action of a magnetic field with system, uses water and washing with alcohol, drying respectively;
(2) seed swelling copolymerization:
I, the single dispersing seed microballoon of preparation is suspended in the aqueous solution containing tensio-active agent and stablizer, adds a small amount of non-proton organic solvent, nitrogen deoxygenation, rapid stirring even for some time, form stable emulsion A; II, monomer, comonomer and non-proton organic solvent are mixed, slowly join in latex A under nitrogen protection, stirring is carried out fully swelling, forms emulsion B;
III, after adding initiator in emulsion B, system is heated to polymerization temperature and is polymerized to and reacts completely, after having reacted, under additional the action of a magnetic field, by product separation, with dehydrated alcohol and acetone supersound washing repeatedly, low-temperature vacuum drying obtains product.
2. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: the described silane reagent containing double bond group is methacrylic acid-3-(trimethoxysilyl) propyl ester or vinyltrimethoxy silane; Described monomer is the hydrocarbon monomer that side chain contains phenyl ring; Comonomer is N-V-Pyrol RC, acrylate or methyl methacrylate.
3. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: described stablizer is water-soluble cellulose ether, Polyvinylpyrolidone (PVP) or Vltra tears; Tensio-active agent is negatively charged ion, positively charged ion or nonionic surface active agent; Described non-protonic solvent is toluene, normal heptane, normal hexane or whiteruss.
4. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: described initiator position benzoyl peroxide, t-butyl per(oxy)benzoate or Diisopropyl azodicarboxylate.
5. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: described Fe
3o
4siO
2particle diameter be 50nm ~ 2 μm.
6. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: in described step (1), the hydrolysis temperature of silane reagent is 50 ~ 80 DEG C.
7. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: the condensation reaction time in described step (1) is 4 ~ 12 hours.
8. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: in described step (2) the Ith step, the weight percent of seed microballoon, tensio-active agent, stablizer, water, non-proton organic solvent is: (1.2 ~ 1.8): (4 ~ 6): (0.8 ~ 1.2): (560 ~ 840): (8 ~ 12); In IIth step and III, the weight percent of monomer, comonomer, non-proton organic solvent and initiator is: (4.5 ~ 7.5): (4 ~ 6): (7 ~ 11): (0.1 ~ 1.5).
9. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: in described step (2) the Ith step, churning time is 3 ~ 20 hours, and the emulsion made is not stratified.
10. superparamagnetism Premium Features polymkeric substance mono-dispersion microballoon according to claim 1, is characterized in that: stirring the swelling time in described step (2) the IIth step is 2 ~ 12 hours, and the emulsion made is not stratified.
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| CN108956918A (en) * | 2018-06-11 | 2018-12-07 | 安徽省佳逸环保科技有限公司 | It is a kind of for being enriched with the concentration detection method of the preparation method of the magnetic film materials of organophosphorus pesticide and organophosphorus pesticide in water body |
| CN110133161A (en) * | 2019-05-31 | 2019-08-16 | 浙江省农业科学院 | Pre-treating method based on more pesticide residues in modified magnetic nano material measurement seasoning vegetable |
| CN113083177A (en) * | 2021-02-24 | 2021-07-09 | 苏州为度生物技术有限公司 | Magnetic fluorescent microsphere with core-shell structure and preparation method thereof |
| CN113578214A (en) * | 2021-08-11 | 2021-11-02 | 天津博蕴纯化装备材料科技有限公司 | Micron-sized porous magnetic microsphere and preparation method and application thereof |
| CN114106266A (en) * | 2021-11-25 | 2022-03-01 | 东南大学 | Raspberry-shaped magnetic polystyrene microsphere and preparation method thereof |
| CN115228450A (en) * | 2022-07-12 | 2022-10-25 | 南京大学 | Preparation method of magnetic ester-based resin with uniform particle size |
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| CN108956918A (en) * | 2018-06-11 | 2018-12-07 | 安徽省佳逸环保科技有限公司 | It is a kind of for being enriched with the concentration detection method of the preparation method of the magnetic film materials of organophosphorus pesticide and organophosphorus pesticide in water body |
| CN108956918B (en) * | 2018-06-11 | 2022-01-11 | 安徽省佳逸环保科技有限公司 | Preparation method of magnetic film material for enriching organophosphorus pesticide in water body and concentration detection method of organophosphorus pesticide |
| CN110133161A (en) * | 2019-05-31 | 2019-08-16 | 浙江省农业科学院 | Pre-treating method based on more pesticide residues in modified magnetic nano material measurement seasoning vegetable |
| CN110133161B (en) * | 2019-05-31 | 2021-09-17 | 浙江省农业科学院 | Pretreatment method for determining multiple pesticide residues in seasoned vegetables based on modified magnetic nano material |
| CN113083177A (en) * | 2021-02-24 | 2021-07-09 | 苏州为度生物技术有限公司 | Magnetic fluorescent microsphere with core-shell structure and preparation method thereof |
| CN113578214A (en) * | 2021-08-11 | 2021-11-02 | 天津博蕴纯化装备材料科技有限公司 | Micron-sized porous magnetic microsphere and preparation method and application thereof |
| CN113578214B (en) * | 2021-08-11 | 2023-08-11 | 天津博蕴纯化装备材料科技有限公司 | Micron-sized porous magnetic microsphere and preparation method and application thereof |
| CN114106266A (en) * | 2021-11-25 | 2022-03-01 | 东南大学 | Raspberry-shaped magnetic polystyrene microsphere and preparation method thereof |
| CN115228450A (en) * | 2022-07-12 | 2022-10-25 | 南京大学 | Preparation method of magnetic ester-based resin with uniform particle size |
| CN115228450B (en) * | 2022-07-12 | 2023-10-17 | 南京大学 | Preparation method of magnetic ester-based resin with uniform particle size |
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