CN101882495B - Nano Fe3O4/ polystyrene-maleic anhydride magnetic hybrid material and preparation method thereof - Google Patents

Nano Fe3O4/ polystyrene-maleic anhydride magnetic hybrid material and preparation method thereof Download PDF

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CN101882495B
CN101882495B CN2009100226168A CN200910022616A CN101882495B CN 101882495 B CN101882495 B CN 101882495B CN 2009100226168 A CN2009100226168 A CN 2009100226168A CN 200910022616 A CN200910022616 A CN 200910022616A CN 101882495 B CN101882495 B CN 101882495B
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tempo
maleic anhydride
hours
tetramethyl
polystyrene
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CN101882495A (en
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王云普
李宏军
陈久存
卢全
魏铄蕴
颜小东
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Northwest Normal University
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Abstract

The invention discloses a nano Fe3O4/ polystyrene-maleic anhydride magnetic hybrid material and a preparation method thereof. The preparation method comprises the following steps of: preparing Fe3O4 nano particles; dissolving 2,2,6,6-tetramethyl-1-piperidine oxide (TEMPO) into carbon tetrachloride and liquid bromine to prepare 2,2,6,6-tetramethyl-1-piperidine oxide bromine salt (Br-TEMPO); dissolving the 2,2,6,6-tetramethyl-1-piperidine oxide bromine salt (Br-TEMPO) and the Fe3O4 nano particles into dichloromethane respectively, and adding triethylamine into the solution to prepare 2,2,6,6-tetramethyl-1-piperidine oxide modified Fe3O4 (Fe-O-TEMPO); and ultrasonically dispersing Fe-O-TEMPO into styrene, and then adding maleic anhydride and N,N-dimethyl formamide into the solution to prepare the nano Fe3O4/ polystyrene-maleic anhydride magnetic hybrid material. Different from common magnetic material modification, a polymer is grafted on the surface of the magnetic material, and the molecular weight of the polymer is controllable.

Description

A kind of nanometer Fe＜sub〉3＜/sub〉O＜sub〉4＜/sub 〉/polystyrene-maleic anhydride magnetic hybrid material and preparation method thereof
Technical field
The present invention relates to a kind of magnetic hybrid material and preparation method thereof, particularly nanometer Fe 3O 4/ polystyrene-maleic anhydride magnetic hybrid material and preparation method thereof.
Background technology
By means such as copolymerization and surface modification make the magnetic material surface contain various functional groups (as-COOH ,-NH 2,-OH ,-SO 3H reaches-CH 3Deng), thereby make it have activity, can combine with bioactivators such as enzyme, protein, nucleic acid, antibody, antigen and cells, therefore this microballoon is widely used in fields such as biochemistry and biomedicine; Again because this material has magnetic, under the action of a magnetic field, can be used as a kind of special separation or location carrier, so important effect is all arranged in cell separation, immobilised enzymes, immunodiagnosis, targeted drug, magnetic shielding material and as the aspects such as carrier of catalyst.
Document " An Lijuan, Li Zhaoqiang, Wang Yanping, Yang Bai, the synthetic Fe of atom transfer radical polymerization method is caused on the surface 3O 4/ PMMA composite nano particle.SCI 2006,27 (7): 1372～1375 " disclose and adopted the surface to cause the magnetic high-molecular nanoparticle that atom transfer radical polymerization method has synthesized nucleocapsid structure, with the Fe of initiators for polymerization 3-chloropropionic acid and oleic acid modified 3O 4The part oleic acid displacement of nano-particle surface is then at Fe 3O 4Nano-particle surface causes methyl methacrylate polymerization.
Document " Liu Chunli, Zhou Fugui, Han Zhaorang, Cui Linlin, Yu Na, Li Yu, the preparation and the sign of poly-(styrene-propene acid) magnetic macromolecular microsphere, chemical research 2007,18 (4): 72-75 " discloses a kind of Fe that utilizes the double-layer surface-active agent modification 3O 4Magnetic fluid is a seed, has prepared styrene-propene acid by emulsion polymerization and has coated Fe 3O 4Magnetic microsphere.
The synthesizing magnetic material of above-mentioned bibliographical information, no matter be grafting or physics coats, they adopt conventional free radical polymerisation process, the shell polymer molecular weight is wayward, and mostly be Van der Waals force and hydrogen bond combination between macromolecular chain and inorganic particulate, interaction force a little less than, the particulate adhesion that obtains is poor, particle diameter is big, and magnetic content is low.
Summary of the invention
In view of above-mentioned, the objective of the invention is to disclose a kind of nanometer Fe 3O 4/ polystyrene-maleic anhydride magnetic hybrid material and preparation method thereof utilizes this method to prepare the controlled Fe of polymer molecular weight 3O 4Magnetic hybrid material.Carboxyl-content height in this hybrid material, and molecular weight is controlled, this hybrid material is widely used at aspects such as vacuum seal, lubricated, magnetic recording, targeted drug and biotechnologys.
Purpose of the present invention can be finished by the following technical programs:
A kind of nanometer Fe 3O 4The preparation method of/polystyrene-maleic magnetic hybrid material comprises the following steps:
A. a certain proportion of Iron trichloride hexahydrate and ferrous sulfate heptahydrate are mixed, be presented to there-necked flask, put into magneton; stirring on oil bath pan mixes it; add proper ammonia again in flask, nitrogen protection is under 20 ℃～35 ℃; stir speed (S.S.) is 600～3000 rev/mins; react and be heated to 70～90 ℃ after 30～60 minutes, reacted 4～8 hours, cooling; separate with alnico magnets, obtain 20 nano-magnetic Fe 3O 4
B. with 2,2,6,6-tetramethyl-1-piperidine oxide (TEMPO) is dissolved in the carbon tetrachloride, and the liquid feeding bromine reacted 30～60 minutes, filter, with carbon tetrachloride washing for several times, till washing lotion is colourless, 40 ℃ of vacuumize 24～48 hours, obtain 2,2,6,6-tetramethyl-1-piperidine oxide bromine salt (Br-TEMPO);
C. with the Fe that obtains among the step a 3O 4Particle is dissolved in the 20mL carrene, 40mL having been dissolved the Br-TEMPO drips of solution that step b obtains adds again, add triethylamine, reacted 24～48 hours down, filter at 20～40 ℃, with carrene and deionized water wash 4 times, in room temperature vacuumize, obtain 2,2,6, the Fe that 6-tetramethyl-1-piperidine oxide is modified 3O 4(Fe-O-TEMPO);
D. the material that step c is obtained joined in the styrene, and ultrasonic dispersion 30 minutes adds maleic anhydride again, adds N, and dinethylformamide stirs, 110～130 ℃ of reactions 0.5～8.0 hour;
E. the product that steps d is obtained is with the oxolane dissolving, centrifugal at 5000 rev/mins centrifuge;
F. in beaker, add the supernatant that absolute ethyl alcohol takes settling step e to obtain, filter, 50 ℃ of vacuumizes 24 hours;
G. the solid that obtains of step f is 50 ℃ of vacuumizes, with oxolane extracting 48～72 hours;
H. the product with step g obtained nanometer Fe in 24～72 hours at the room temperature vacuum drying 3O 4/ polystyrene-maleic anhydride magnetic hybrid material.
The nanometer Fe that obtains 3O 4/ polystyrene-maleic anhydride magnetic hybrid material is through infrared, thermal weight loss, gel permeation chromatography (GPC), transmission electron microscope (TEM), magnetic hysteresis loop analysis.The infrared spectrum of magnetic hybrid material shows, at 568cm -1(Fe 3O 4), 1079cm -1, 924cm -1, 698cm -1(polystyrene) located absworption peak, at 1702cm -1Occur outside the carbonyl absorption peak, also at about 1778cm -1Another characteristic absorption peak (maleic anhydride) of carbonyl on the anhydride rings appears in the place, and the copolymer grafted that styrene and maleic anhydride are described is to Fe 3O 4Can obtain from transmission electron microscope, not have the Fe of grafting 3O 4Granular size is in 20 to 30 nanometers, and is most of in the 50-100 nanometer after the grafting, and disperses better.The specific saturation magnetization of magnetic microsphere is 28.2emu/g.This illustrates that this experiment is grafted to Fe with styrene and maleic anhydride 3O 4
The advantage of the method is: the molecular weight of controlling graft polymers by controlling reaction time, can control the size of molecular weight by controllable polymerization, thereby control grafting amount, especially the maleic anhydride that contains acid anhydrides, can reach the control carboxyl what, aspects such as the sealing of this against vacuum, lubricated, magnetic recording, targeted drug and biotechnology are all very important.The method is when the preparation magnetic hybrid material, and method is simple, and conditional request is low, and raw material is easy to get, and DEVELOPMENT PROSPECT is arranged very much.
Description of drawings
Fig. 1 is the hot weightless picture that embodiment 3 obtains.
Fig. 2 is the magnetic microsphere transmission electron microscope that embodiment 3 obtains.
Embodiment
Below, again technical scheme of the present invention is illustrated in the mode of embodiment:
Embodiment 1
A kind of nanometer Fe 3O 4The preparation method of/polystyrene-maleic magnetic hybrid material comprises the following steps:
A. ferrous sulfate heptahydrate is water-soluble stirs with 27.0 gram Iron trichloride hexahydrates and 13.9 grams, inserts in the 500mL there-necked flask, puts into magneton; stirring mixes it on oil bath pan, adds an amount of 22% concentrated ammonia liquor, nitrogen protection again in flask; make PH=10, under 25 ℃, stir speed (S.S.) is at 800 rev/mins; react and be heated to 75 ℃ after 50 minutes, reacted 8 hours, cooling; filter; water and ethanol washing, vacuumize obtains Fe with the alnico magnets separation 3O 4Nano particle;
B. with 2.5 grams 2,2,6,6-tetramethyl-1-piperidine oxide (TEMPO) is dissolved in the 100mL carbon tetrachloride, adds 3.2 gram liquid bromines, reacts 40 minutes, filter, with carbon tetrachloride washing for several times, till washing lotion is colourless, 40 ℃ of vacuumize 24 hours, obtain 2,2,6,6-tetramethyl-1-piperidine oxide bromine salt (Br-TEMPO);
C. the Fe that step a is obtained 3O 4Particle 0.25 gram is dissolved in the 20mL carrene, the 40mL that step b the is obtained Br-TEMPO drips of solution of having dissolved 0.9 gram is added again, add the 0.15mL triethylamine, reacted 48 hours down, filter at 30 ℃, with 8mL carrene and 10mL deionized water wash 4 times, in room temperature vacuumize, obtain 2,2,6, the Fe that 6-tetramethyl-1-piperidine oxide is modified 3O 4(Fe-O-TEMPO);
D. Fe-O-TEMPO 0.07 gram that step c is obtained joins in the 6.0mL styrene, and ultrasonic dispersion 30 minutes adds 0.41 gram maleic anhydride again, adds 0.2mL N, and dinethylformamide stirred, 126 ℃ of reactions 0.5 hour;
E. the product that steps d is obtained is with the dissolving of 5mL oxolane, centrifugal at 5000 rev/mins centrifuge;
F. in the 500mL beaker, add the supernatant that the 150mL absolute ethyl alcohol takes settling step e to obtain, filter, 50 ℃ of vacuumizes;
G. the solid that obtains of step f. is 50 ℃ of vacuumizes, with oxolane extracting 48 hours;
H. the product with step g obtained nanometer Fe in 24～72 hours at the room temperature vacuum drying 3O 4/ polystyrene-maleic anhydride magnetic hybrid material.
Embodiment 2:
Fe 3O 4Nano particle, example 1 step a makes.
With 3.0 grams 2,2,6,6-tetramethyl-1-piperidine oxide (TEMPO) is dissolved in the 100mL carbon tetrachloride, adds 3.8 gram liquid bromines, reacts 50 minutes, filter, with carbon tetrachloride washing for several times, till washing lotion is colourless, 40 ℃ of vacuumize 24 hours, obtain 2,2,6,6-tetramethyl-1-piperidine oxide bromine salt (Br-TEMPO);
With Fe 3O 4Particle 0.30 gram is dissolved in the 20ml carrene, and the Br-TEMPO drips of solution of again 40mL having been dissolved 1.2 grams is added, and adds the 0.20ml triethylamine, reacted 48 hours down at 35 ℃, filter, use 8mL carrene and 10mL deionized water wash 5 times, in room temperature vacuumize, obtain Fe-O-TEMPO).
Fe-O-TEMPO 0.1 gram is joined in the 6.0mL styrene, and ultrasonic dispersion 30 minutes adds 0.43 gram maleic anhydride again, adds 0.2mL N, dinethylformamide.Stir, 126 ℃ of reactions 1 hour.With the dissolving of 5mL oxolane, centrifugal, oven dry, oxolane extracting 48 hours obtained nanometer Fe in 24～72 hours at the room temperature vacuum drying 3O 4/ polystyrene-maleic anhydride magnetic hybrid material.
Embodiment 3:Fe 3O 4Nano particle, Br-TEMPO, Fe-O-TEMPO such as example 1 step a, step b, step c make.
Then Fe-O-TEMPO 0.07 gram is joined in the 5.0mL styrene, ultrasonic dispersion 30 minutes adds 0.41 gram maleic anhydride again, adds 0.2mLN, dinethylformamide.Stir, 126 ℃ of reactions 2 hours.With the dissolving of 5mL oxolane, centrifugal, oven dry, oxolane extracting 48 hours obtained nanometer Fe in 24～72 hours at the room temperature vacuum drying 3O 4/ polystyrene-maleic anhydride magnetic hybrid material.
With embodiment 3 is example, does one group of experiment in 0.5,1.0,1.5,2.0 hour as the time is made as, and obtains following result:
Time (hour) Number-average molecular weight Weight average molecular weight Molecular weight distribution
0.5 43784 47724 1.09
1.0 58823 65587 1.11
1.5 105449 118102 1.12
2.0 180861 202564 1.12
The data enumerated as can be seen from table: molecular weight distribution is narrow, and controlling reaction time is controlled the molecular weight of graft polymers.Percent grafting shown in Figure 1 is 33.5%, and Fig. 2 obtains the Fe by 20 nanometers 3O 4Increase to 50～200 nanometers, illustrate that the polymers grafted amount is still very big, is consistent with Fig. 1.
Embodiment 4:Fe 3O 4Nano particle, Br-TEMPO, Fe-O-TEMPO such as example 1 step a, step b, step c make.
Fe-O-TEMPO 0.07 gram is joined in the 5.0mL styrene, and ultrasonic dispersion 30 minutes adds 0.41 gram maleic anhydride again, adds 0.2mLN, dinethylformamide.Stir, 126 ℃ of reactions 4 hours.With the dissolving of 5mL oxolane, centrifugal, oven dry, oxolane extracting 48 hours obtains nanometer Fe at the room temperature vacuum drying 3O 4/ polystyrene-maleic anhydride magnetic hybrid material.
The embodiment that the present invention lists, according to the requirement of actual application difference, the method advantage is different.Such as wanting the macromolecular example 4 that then needs; That wants the magnetic strong point then needs example 1; What condition was more excellent in synthetic if desired then is that embodiment 3. is shorter because of this condition experiment time, and polymerization effect is better, and molecular weight is of moderate size.Though the material magnetic that embodiment 1,2 obtains is stronger, molecule is less, and conversion ratio is less; Example 4, then molecular weight is bigger, the serious bad dispersion of agglomeration.

Claims (1)

1. nanometer Fe 3O 4The preparation method of/polystyrene-maleic anhydride magnetic hybrid material comprises the following steps:
A. a certain proportion of Iron trichloride hexahydrate and ferrous sulfate heptahydrate are mixed, be presented to there-necked flask, put into magneton; stirring on oil bath pan mixes it; add proper ammonia again in flask, nitrogen protection is under 20 ℃～35 ℃; stir speed (S.S.) is 600～3000 rev/mins; react and be heated to 70～90 ℃ after 30～60 minutes, reacted 4～8 hours, cooling; separate with alnico magnets, obtain 20 nano-magnetic Fe 3O 4Particulate;
B. with 2,2,6,6-tetramethyl-1-piperidine oxide (TEMPO) is dissolved in the carbon tetrachloride, and the liquid feeding bromine reacted 30～60 minutes, filter, with carbon tetrachloride washing for several times, till washing lotion is colourless, 40 ℃ of vacuumize 24～48 hours, obtain 2,2,6,6-tetramethyl-1-piperidine oxide bromine salt (Br-TEMPO);
C. with the Fe that obtains among the step a 3O 4Particulate is dissolved in the 20mL carrene, 40mL having been dissolved the Br-TEMPO drips of solution that step b obtains adds again, add triethylamine, reacted 24～48 hours down, filter at 20～40 ℃, with carrene and deionized water wash 4 times, in room temperature vacuumize, obtain 2,2,6, the Fe that 6-tetramethyl-1-piperidine oxide is modified 3O 4(Fe-O-TEMPO);
D. the material that step c is obtained joined in the styrene, and ultrasonic dispersion 30 minutes adds maleic anhydride again, adds N, and dinethylformamide stirs, 110～130 ℃ of reactions 0.5～8.0 hour;
E. the product that steps d is obtained is with the oxolane dissolving, centrifugal at 5000 rev/mins centrifuge;
F. in beaker, add the supernatant that absolute ethyl alcohol takes settling step e to obtain, filter, 50 ℃ of vacuumizes 24 hours;
G. the solid that obtains of step f is 50 ℃ of vacuumizes, with oxolane extracting 48～72 hours;
H. the product with step g obtained nanometer Fe in 24～72 hours at the room temperature vacuum drying 3O 4/ polystyrene-maleic anhydride magnetic hybrid material.
CN2009100226168A 2009-05-09 2009-05-09 Nano Fe3O4/ polystyrene-maleic anhydride magnetic hybrid material and preparation method thereof Expired - Fee Related CN101882495B (en)

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CN104497234A (en) * 2014-12-12 2015-04-08 同济大学 Preparation method of magnetic hybrid material with UCST (utmost critical solution temperature)
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CN109422826B (en) * 2017-09-05 2020-12-18 中国石油化工股份有限公司 Method for separating polymer product by using superfine polymer dispersion system with organic phase as dispersion medium

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101183590A (en) * 2007-09-30 2008-05-21 华东师范大学 Malic acid coating water-based magnetic fluid material and production thereof
CN101209860A (en) * 2007-12-25 2008-07-02 哈尔滨师范大学 Method for preparing water-based Fe3O4 magnetic fluid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101183590A (en) * 2007-09-30 2008-05-21 华东师范大学 Malic acid coating water-based magnetic fluid material and production thereof
CN101209860A (en) * 2007-12-25 2008-07-02 哈尔滨师范大学 Method for preparing water-based Fe3O4 magnetic fluid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘春丽 等.Fe3O4/聚苯乙烯磁性微球的合成与表征.《高分子材料科学与工程》.2008,第24卷(第3期),137-140. *
章永化 等.纳米Fe3O4/聚苯乙烯均匀分散体系的制备及结构.《高等学校化学学报》.2003,第24卷(第9期),1717-1720. *

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