CN103289102A - Dual-response magnetic nano particle with fluorescence and preparation method thereof - Google Patents
Dual-response magnetic nano particle with fluorescence and preparation method thereof Download PDFInfo
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- CN103289102A CN103289102A CN201310228616XA CN201310228616A CN103289102A CN 103289102 A CN103289102 A CN 103289102A CN 201310228616X A CN201310228616X A CN 201310228616XA CN 201310228616 A CN201310228616 A CN 201310228616A CN 103289102 A CN103289102 A CN 103289102A
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Abstract
The invention discloses a dual-response magnetic nano particle with fluorescence and a preparation method thereof, belonging to the technical field of functional polymer materials. An existing response magnetic nano particle is smaller in response range and is incapable of tracing mark. A chemical expression formula of the magnetic nano particle is Fe3O4@M(III)-(PNIPAMm-b-PAzoMAn)-TTA (PNIPAM (Poly(N-isopropylacrylamide) and TTA (thenoyltrifluoroacetone), wherein M is Eu<3+>, Tb<3+>, Sm<3+> or Er<3+>, m is equal to 42-132, and n is equal to 5-20. AzoMA and NIPAM (N-isopropylacrylamide) are polymerized to an RAFT (Reversible Addition-Fragmentation chain Transfer) chain transfer agent through an RAFT free radical polymerization method, and M(III)-(PNIPAMm-b-PAzoMAn)-TTA is obtained through a coordination reaction, and then is modified to the surface of a ferriferrous oxide nano particle through an esterification reaction. The dual-response magnetic nano particle is capable of carrying out magnetic separation under the control of the temperature and the light, and has a potential application value in the aspects of biological marking, imaging, artificial muscle and the like.
Description
Technical field
The present invention relates to a kind of epipolic double-response type magnetic nano-particle and preparation method thereof that has, utilization has the temperature sensitive property of epipolic rare earth ion, nitrogen N-isopropylacrylamide and the sensitivity of light of azobenzene compound, and the fabulous superparamagnetism of Z 250, prepare multiple environment response type polymer material, belong to the functional high molecule material technical field.
Background technology
A series of variations such as the temperature that environmental response type macromolecular material can perception comes from the outside, pH, magnetic, light, electric field.According to its this character of characteristic variations under specific environment, environmental response type macromolecular material can be applied to many fields, such as fixing, the aspect such as protein is fixing of: artificial muscle, target medicament slow release, memory cell switch, sensor, chemical storage device, biomarker, molecular separation system, organizational project, enzyme.
Z 250 is owing to have fabulous superparamagnetism, fixes at target medicament slow release, protein, there is potential using value aspects such as magnetic separation, thermotherapy, mr photographic developer.But because pure Fe
3O
4Agglomeration takes place easily and can not directly using, need carry out modification to its surface.Up to the present, people are to Fe
3O
4The surface carry out modification, concrete grammar is earlier the chain-transfer agent of reversible addition cracking chain transferring free-radical polymerization (RAFT) to be modified Fe by electrostatic interaction
3O
4The surface; Then, utilize the RAFT polyreaction to introduce NIPAM, and aldehyde material or other material that can identification of protein, synthetic magnetic nanoparticle with temperature sensitive property.The magnetic nanoparticle of above-mentioned temperature sensitive property separates or protein is fixing etc. that the aspect has shown good using value at medicament slow release, magnetic, but its responsiveness scope is narrow, can not more stimulate to external world to tackle, and can not radioactive labelling.
Summary of the invention
In order to obtain a kind of responsiveness a wider range, can in maximum range, can respond to external environment and make certain responding ability, and can carry out trace labelling to it by fluorescence, we have invented a kind of epipolic double-response type magnetic nano-particle and preparation method thereof that has.
The present invention has an epipolic double-response type magnetic nano-particle, it is characterized in that its grain diameter is 30～50nm, and chemical expression is: Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA,
In the formula, M is Eu
3+, Tb
3+, Sm
3+Or Er
3+
PNIPAM
m-b-PAzoMA
nBe the poly-6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide) of the poly-nitrogen N-isopropylacrylamide-b-of segmented copolymer-N-Hexyl methacrylate, m=41～132, n=5～20;
TTA is α-thenoyltrifluoroacetone.
The present invention's the preparation method with epipolic double-response type magnetic nano-particle is a kind of reversible addition cracking chain transfer radical polymerization method, it is characterized in that, at first, RAFT chain-transfer agent and NIPAM reaction obtain PNIPAM macromolecular chain transfer agent; Secondly, described PNIPAM macromolecular chain transfer agent and AzoMA reaction obtain segmented copolymer PNIPAM
m-b-PAzoMA
nThe 3rd, by described segmented copolymer PNIPAM
m-b-PAzoMA
n, trivalent rare earth metals hydrochloride and TTA carry out coordination, obtain high molecular polymer M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA; The 4th, with described high molecular polymer M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA modifies Fe by esterification
3O
4The surface of nano particle obtains final product Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA.
Its technique effect of the present invention is:
Fe provided by the invention
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA is that a kind of particle size is less, and is the nanoparticle of regular spherical, and its grain diameter only is 30～50nm; This nanoparticle is because in magnetic Fe
3O
4Modified the PNIPAM with temperature sensitive property on the surface of nano particle, had the PAzoMA of photosensitivity, and had epipolic trivalent rare earth ions, temperature, light, the magnetic that can sense external environment change, and make certain response, and relatively sensitive more controlled; Have fluorescence property simultaneously concurrently, can carry out trace labelling to it by fluorescence.Are Fe as accompanying drawing 3
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8)-TTA and pure Fe
3O
4Infrared figure, come more as can be seen according to the infrared figure of two materials, 587 places are Fe
3O
4The charateristic avsorption band of last Fe-O is at Fe
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8The charateristic avsorption band of PNIPAM has appearred in 1629 and 1562 places in the infrared curve of)-TTA, illustrates that multipolymer is modified basically to have arrived Fe
3O
4The surface, but content is fewer.Are Fe as accompanying drawing 4
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8The scanning electron microscope diagram of)-TTA as can be seen from the figure comes, and the granule-morphology of the Z 250 of high molecular polymer parcel is spherical basically, and particle size range is substantially about 30nm.
The PNIPAM that preparation method with epipolic double-response type magnetic nano-particle provided by the invention prepares
m-b-PAzoMA
nBe segmented copolymer, controllability is good, and molecular weight distribution is narrow, heterogeneity index PDI=1.06-1.20; Because PAzoMA is hydrophobic grouping, PNIPAM is influenced by it, and lower critical solution temperature (LCST) obviously reduces; This preparation method prepares Fe simultaneously
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
nThe magnetic of)-TTA can be preserved for a long time and do not disappeared, its magnetic and pure Fe
3O
4The magnetic gap be not very big.
The present invention is had epipolic double-response type magnetic nano-particle to be used in and can to make artificial muscle as the muscle of human body self in the artificial muscle, a series of responsiveness is made in the stimulation of environment generation to external world, by fluorescence it is carried out tracking monitor simultaneously, can separate by magnetic at last these separating substances are removed.
Description of drawings
Fig. 1 be the DMP(curve a) and DMP-PNIPAM(curve b) infrared spectrogram;
Fig. 2 is segmented copolymer PNIPAM
132-b-PAzoMA
8The hydrogen nuclear magnetic resonance spectrogram;
Fig. 3 is Fe
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8)-TTA(curve a) and pure Fe
3O
4The infrared spectrogram of (curve b);
Fig. 4 is Fe
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8The scanning electron microscope diagram of)-TTA, this figure is simultaneously as Figure of abstract.
Embodiment
The present invention's the epipolic double-response type magnetic nano-particle that has is that a kind of grain diameter is the regular spherical nanoparticle of 30～50nm, and its chemical expression is: Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA, in the formula, M is Eu
3+, Tb
3+, Sm
3+Or Er
3+PNIPAM
m-b-PAzoMA
nBe the poly-6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide) of the poly-nitrogen N-isopropylacrylamide-b-of segmented copolymer-N-Hexyl methacrylate, m=41～132, n=5～20; TTA is α-thenoyltrifluoroacetone;
The present invention's the preparation method with epipolic double-response type magnetic nano-particle does and specifies.
At first, RAFT chain-transfer agent and NIPAM reaction obtain PNIPAM macromolecular chain transfer agent.Detailed process is as follows:
The preparation of a, RAFT chain-transfer agent
With mercaptan (RSH, wherein R is alkyl), acetone, Tetrabutyl amonium bromide join in the reaction flask, ice bath leads to nitrogen, adds a certain amount of NaOH and continues to stir, and then adds the acetone soln of CS2, reaction continues to stir, and adds chloroform and NaOH again, then stirs and spends the night; Add deionized water and hydrochloric acid with the noxious solvent in the volatiling reaction, filter, and thick product is dissolved in Virahol, recrystallization in normal hexane obtains required RAFT chain-transfer agent at last; Reaction formula is:
The preparation of b, PNIPAM macromolecular chain transfer agent
Get a certain amount of RAFT chain-transfer agent, NIPAM, CTA, 1,3,5-trioxane and AIBN are dissolved in the dry DMF, behind the logical nitrogen, place oil bath to react reaction flask; After question response is finished, open bottle stopper reaction solution is exposed to termination reaction in the air; The vacuum rotary steam desolventizing, the polymkeric substance that obtains precipitates in anhydrous diethyl ether, and triplicate obtains PNIPAM macromolecular chain transfer agent; Reaction formula is as follows:
Secondly, described PNIPAM macromolecular chain transfer agent and AzoMA reaction obtain segmented copolymer PNIPAM
m-b-PAzoMA
nDetailed process is as follows:
C, [6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide)-N-Hexyl methacrylate] preparation (AzoMA)
At first be with NaNO
2Be dissolved in the deionized water, resulting drips of solution be added in the hydrochloric acid soln of 4-phenetidine, continue to stir, hydrochloric acid must be excessive in this process; Then resultant azo solution is slowly added the NaOH solution of phenol and then stirring, the filemot suspended substance acidifying that obtains is also filtered, filter cake reaches 7 with the pH that deionized water washs up to filtrate, with the second alcohol and water crude product is carried out recrystallization, vacuum-drying obtains 4-hydroxyl-4 ˊ oxyethyl group nitrogen benzide (HEAB);
Then get certain amount of H EAB and 1,6-dibromo-hexane and anhydrous K
2CO
3, under the magnetic agitation state, join in the acetone soln mixture back flow reaction; After reaction is finished, heat filtering, inorganic residue is washed with acetone, collect filtrate, remove acetone soln, residual extract is poured in the sherwood oil and is precipitated, recrystallization twice in ethyl acetate, obtains the 1-Br-6-(hexane (BrEAB) of 4-oxyethyl group nitrogen benzide-4 ˊ-O);
With a certain amount of α-Jia Jibingxisuan and KHCO
3Join among the DMF, under the state that stirs, add BrEAB, revolve after the reaction to steam and remove organic solvent, cross silica gel column chromatography product is purified, obtain [6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide)-N-Hexyl methacrylate] (AzoMA);
Reaction formula is as follows:
D, segmented copolymer PNIPAM
m-b-PAzoMA
nPreparation
A certain amount of AzoMA, PNIPAM macromolecular chain transfer agent, AIBN are dissolved in the dry-out benzene methyl ether, and logical nitrogen 15min reacts in the oil bath of 70 ° of C-80 ° of C, takes out different samples at set intervals and carries out the GPC test, after question response is finished, uses CH
2Cl
2Dilute reaction solution, and in 30 ° of C-60 ° of C sherwood oils, precipitate, after the filtration, obtain segmented copolymer PNIPAM
m-b-PAzoMA
nReaction formula is as follows:
The 3rd, by described segmented copolymer PNIPAM
m-b-PAzoMA
n, trivalent rare earth metals hydrochloride and TTA carry out coordination, obtain high molecular polymer M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA.Detailed process is as follows:
E, with a certain amount of segmented copolymer PNIPAM
m-b-PAzoMA
nPlace tool plug bottle, respectively according to mass ratio M
3+: PNIPAM=0.07:1, mol ratio TTA:M
3+=2 usefulness transfer pipets are got quantitative MCl respectively
3Ethanolic soln and TTA ethanolic soln add the dehydrated alcohol constant volume at last to tool plug bottle; Bottle put under the room temperature react 48h, handle with DMF dialysis (MWCO, 10000), vacuum-drying 24h under 40 ° of C, sub-polymkeric substance M (III)-(PNIPAM secures satisfactory grades
m-b-PAzoMA
n)-TTA.Reaction formula is as follows:
The 4th, with described high molecular polymer M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA modifies Fe by esterification
3O
4The surface of nano particle obtains final product Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA.Detailed process is as follows:
F, Fe
3O
4The preparation of nanoparticle
With FeCl
36H
2O and FeSO
47H
2O is dissolved in the deionized water, under the atmosphere of nitrogen reaction flask is placed water-bath, is heated to 70 ℃ gradually, violent stirring, and slow adding massfraction is 25% ammoniacal liquor 30ml when temperature is raised to 65 ℃, reaction solution is immediately by the orange black that becomes; The throw out of black is at 85 ℃ of following slaking 40min, and with a large amount of deionized water wash for several times, magnetic separates; At last throw out is dispersed in the ethanol, the washing several, magnetic separates; The product that obtains is put into dry 12h in the vacuum drying oven, obtains Fe
3O
4Nanoparticle.
G, Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
nThe preparation of)-TTA
With a certain amount of Fe
3O
4Nanoparticle is dissolved in the dry DMF, and ultrasonic 15min adds M (III)-(PNIPAM of a certain amount of ratio then
m-b-PAzoMA
n)-TTA and EDCHCl and DMAP place the oil bath of 80 ° of C to react 24h reaction flask, and magnetic separates, and constantly wash with excessive methyl alcohol and remove unreacted polymkeric substance, behind the dry 12h, obtain final product Fe in the vacuum drying oven of 40 ° of C
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA.Reaction formula is as follows:
Illustrate the present invention's method below.
At first, RAFT chain-transfer agent and NIPAM reaction obtain PNIPAM macromolecular chain transfer agent.
The preparation of a, RAFT chain-transfer agent
20mmol lauryl mercaptan, the Tetrabutyl amonium bromide of 0.8mmol are dissolved in the 10ml acetone, feed nitrogen 30min under the ice bath, are that 50% NaOH slowly adds then with the massfraction of 1.68g.Behind the reaction 15min, add a certain amount of CS
2Acetone soln (CS
2: 20mmol; Acetone: 34.5mmol).Then continue to stir 15min, add 30ml chloroform and 8g NaOH, remove the continuation reaction behind the ice bath 30min and spend the night.The hydrochloric acid that adds 30ml deionized water and 5ml is removed organic solvent, yellow thick product appears, suction filtration, under violent stirring, thick product is dissolved in the Virahol of 100ml, Virahol is removed in the decompression dissolving, in normal hexane, behind the recrystallization, obtain required RAFT chain-transfer agent S-dodecyl-S'-(2-methyl-2-propionyloxy) trithiocarbonate.
The preparation of b, PNIPAM macromolecular chain transfer agent
With 11.2mmol NIPAM, 0.056mmol CTA, 0.56mmol1,3,5-trioxane, 0.011mmol AIBN, be dissolved among the 8mLDMF, logical nitrogen 15min, reaction flask places 70 ℃ oil bath pan to react, take out different samples at set intervals and carry out the GPC test, choose the molecular weight suitable polymers.After question response is finished, open bottle stopper reaction solution is exposed to termination reaction in the air.The vacuum rotary steam desolventizing, resulting polymkeric substance precipitates in ether, and triplicate obtains PNIPAM macromolecular chain transfer agent.Reaction formula is as follows:
Fig. 1 is the infrared spectrogram of DMP, DMP-PNIPAM, from the infrared figure of DMP, comes as can be seen, and the 2950th, the antisymmetric stretching vibration peak of methyl, 2920 and 2851 are in the dodecyl-CH
2-CH
2-unsymmetrically and symmetrical stretching vibration peak, the 1719th, the stretching vibration peak of C=O on the carboxyl, the 1463rd, the stretching vibration peak of the methylene radical that links to each other with sulphur on the dodecyl, the 1281st, the stretching vibration peak of carboxyl (COOH), 1171 and 1070 is stretching vibration peaks of C=S, the stretching vibration peak of the 812nd, C-S, the 720th, CH
2The stretching vibration peak of-S can be judged according to these data and successfully to have synthesized target product DMP; Infrared figure from DMP-PNIPAM comes as can be seen simultaneously, 3308 is vibration performance absorption peaks of secondary amide N-H key on the PNIPAM in DMP-PNIPAM, 1649 stretching vibration peaks for the two keys (acid amides I band) of the last C=O of PNIPAM, 1544 is flexural vibration, acid amides II band (the C-N key stretching vibration coupling absorbs) absorption peak of the N-H key in the amide group; Come as can be seen according to comparing of two figure among Fig. 1, success has obtained PNIPAM macromolecular chain transfer agent according to the RAFT polymerization process.
Secondly, described PNIPAM macromolecular chain transfer agent and AzoMA reaction obtain segmented copolymer PNIPAM
132-b-PAzoMA
8
C, [6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide)-N-Hexyl methacrylate] preparation (AzoMA)
With 218mmolNaNO
2Be dissolved in the deionized water of 100mL, slowly join in the hydrochloric acid soln of 207mmol4-monomethylaniline, the powerful 2h that stirs in the time of 0 ℃, then resulting azo solution is joined in the NaOH solution of phenol of 217mmol, stir 2h, with deionized water resulting precipitation is washed up to filtrate pH and reach 7, (V/V=1/1) carries out recrystallization to crude product with the second alcohol and water, vacuum-drying has namely obtained 4-hydroxyl-4 ˊ oxyethyl group nitrogen benzide (HEAB).
Get above-mentioned prepared 30mmol HEAB, 61mmol1,6-dibromo-hexane, 161mmol anhydrous K
2CO
3Join successively in the acetone soln of 300mL, reaction mixture is heated to 75 ℃ and backflow 24h.After reaction is finished, hot solution is filtered at once, inorganic residue is thoroughly cleaned with the acetone of heat, collect filtrate, vacuum distilling acetone, residual extract is poured into precipitation in the cold sherwood oil (30-60 ℃), and heat filtering recrystallization twice in ethyl acetate has namely obtained the 1-Br-6-(hexane (BrEAB) of 4-oxyethyl group nitrogen benzide-4 ˊ-O).
With 2mmol α-Jia Jibingxisuan and 1molKHCO
3Be dissolved among the 40mLDMF, under the state that stirs, add 1mmolBrEAB, react 4h under 65 ° of C, revolve to steam and remove DMF, cross silica gel column chromatography product is purified, obtain [6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide)-N-Hexyl methacrylate] (AzoMA).
Reaction formula is as follows:
D, segmented copolymer PNIPAM
132-b-PAzoMA
8Preparation
A certain amount of 0.5mmol AzoMA, 0.015mmol PNIPAM macromolecular chain transfer agent, 0.02mmol AIBN are dissolved in the methyl-phenoxide of 5mL, logical nitrogen deoxygenation 15min, react 24h under the 80oC, revolve the steaming desolventizing, with methylene dichloride reaction solution is diluted, in sherwood oil, precipitate, filter and namely obtain segmented copolymer PNIPAM
132-b-PAzoMA
8Reaction formula is as follows:
Fig. 2 is PNIPAM
132-b-PAzoMA
8The hydrogen nuclear magnetic resonance spectrogram, as can be seen from the figure come, in chemical shift δ=7.85, δ=6.93 places are corresponding to the proton absorption peak that is phenyl ring on the nitrogen benzide, δ=7.291 places are that PNIPAM goes up the proton peak that is connected with nitrogen-atoms in the secondary amide base, the proton absorption peak of methyne on the sec.-propyl is gone up at δ=3.858 places corresponding to the proton on the methylene radical that links to each other with Sauerstoffatom on the nitrogen benzide and PNIPAM, δ=3.745 places corresponding on the nitrogen benzide with methyl that Sauerstoffatom links to each other on the proton absorption peak, δ=3.34 places are corresponding to the proton absorption peak of methylene radical on the dodecyl among the DMP, the fignal center of other proton is in the drawings one by one on the correspondence in the multipolymer, each H is well confirmed among the figure, and peak area is directly proportional with corresponding hydrogen number.
The 3rd, by described segmented copolymer PNIPAM
132-b-PAzoMA
8, trivalent rare earth metals hydrochloride and TTA carry out coordination, obtain high molecular polymer Eu (III)-(PNIPAM
132-b-PAzoMA
8)-TTA.
Claim 50mg EuCl
3Be dissolved in the 18mL ethanol, heated and stirred is transparent to solution in 50 ℃ of water-baths, calculates by last liquor capacity.Then with a certain amount of PNIPAM
132-b-PAzoMA
8Place tool plug bottle, respectively according to mass ratio Eu
3+: PNIPAM=0.07:1, mol ratio TTA:Eu
3+=2 usefulness transfer pipets pipette the EuCl of calculated amount respectively
3Ethanolic soln and TTA ethanolic soln add dehydrated alcohol at last and are settled to 10mL to tool plug bottle.Bottle put under the room temperature react 48h, handle with DMF dialysis (MWCO, 10000), vacuum-drying 24h under 40 ° of C gets Eu (III)-(PNIPAM
132-b-PAzoMA
8)-TTA.
Reaction formula is as follows:
With described EuCl
3Be replaced by TbCl
3, SmCl
3Or ErCl
3, the product of this step then is:
Tb (III)-(PNIPAM
132-b-PAzoMA
8)-TTA, Sm (III)-(PNIPAM
132-b-PAzoMA
8)-TTA or Er (III)-(PNIPAM
132-b-PAzoMA
8)-TTA.
The 4th, with described high molecular polymer Eu (III)-(PNIPAM
132-b-PAzoMA
8)-TTA modifies Fe by esterification
3O
4The surface of nano particle obtains final product Fe
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8)-TTA.
F, Fe
3O
4The preparation of nanoparticle
FeCl with 0.0175mmol
36H
2The FeSO of O and 0.01mmol
47H
2O is dissolved in the deionized water of 100ml, under the atmosphere of nitrogen, reaction flask is placed water-bath, be heated to 70 ℃ gradually, violent stirring, slow adding massfraction is 25% ammoniacal liquor 30ml when temperature is raised to 65 ℃, keep the pH of solution to be approximately 10 in the reaction process, reaction solution is immediately by the orange black that becomes.The throw out of black is at 85 ℃ of following slaking 40min, and with a large amount of deionized water wash for several times, magnetic separates; At last throw out is dispersed in the ethanol, the washing several, magnetic separates.The product that obtains places the dry 12h of vacuum drying oven, obtains Fe
3O
4Nanoparticle.
G, Fe
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8The preparation of)-TTA
Fe with 0.06mmol
3O
4Be dissolved in the anhydrous N of 20mL, the dinethylformamide, ultrasonic 15min adds excessive 0.3mmolEu (III)-(PNIPAM then
132-b-PAzoMA
8)-TTA and EDCHCl and DMAP place the oil bath of 80 ° of C to react 24h reaction flask, and magnetic separates, and constantly wash with excessive methyl alcohol and remove unreacted polymkeric substance, and dry 12h obtains Fe in the vacuum drying oven of 40 ° of C
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8)-TTA.Reaction formula is as follows:
Fig. 3 is Fe
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8)-TTA and pure Fe
3O
4Infrared figure, come more as can be seen according to the infrared figure of two materials, 587 places are Fe
3O
4The charateristic avsorption band of last Fe-O is at Fe
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8The charateristic avsorption band of PNIPAM has appearred in 1629 and 1562 places in the infrared curve of)-TTA, illustrates that multipolymer is modified basically to have arrived Fe
3O
4The surface, but content is fewer.Fig. 4 is Fe
3O
4@Eu (III)-(PNIPAM
132-b-PAzoMA
8The scanning electron microscope diagram of)-TTA as can be seen from the figure comes, and the granule-morphology of the Z 250 of high molecular polymer parcel is spherical basically, and particle size range is substantially about 30nm.
Claims (7)
1. have epipolic double-response type magnetic nano-particle, it is characterized in that, its grain diameter is 30～50nm, and chemical expression is: Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA,
In the formula, M is Eu
3+, Tb
3+, Sm
3+Or Er
3+
PNIPAM
m-b-PAzoMA
nBe the poly-6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide) of the poly-nitrogen N-isopropylacrylamide-b-of segmented copolymer-N-Hexyl methacrylate, m=41～132, n=5～20;
TTA is α-thenoyltrifluoroacetone.
2. according to the described preparation method with epipolic double-response type magnetic nano-particle of claim 1, be a kind of reversible addition cracking chain transfer radical polymerization method, it is characterized in that, at first, RAFT chain-transfer agent and NIPAM reaction obtain PNIPAM macromolecular chain transfer agent; Secondly, described PNIPAM macromolecular chain transfer agent and AzoMA reaction obtain segmented copolymer PNIPAM
m-b-PAzoMA
nThe 3rd, by described segmented copolymer PNIPAM
m-b-PAzoMA
n, trivalent rare earth metals hydrochloride and TTA carry out coordination, obtain high molecular polymer M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA; The 4th, with described high molecular polymer M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA modifies Fe by esterification
3O
4The surface of nano particle obtains final product Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA.
3. according to the described preparation method with epipolic double-response type magnetic nano-particle of claim 2, it is characterized in that, RAFT chain-transfer agent and NIPAM reaction, a kind of concrete scheme that obtains PNIPAM macromolecular chain transfer agent is:
The preparation of a, RAFT chain-transfer agent
With mercaptan (RSH, wherein R is alkyl), acetone, Tetrabutyl amonium bromide join in the reaction flask, and ice bath leads to nitrogen, add a certain amount of NaOH and continue to stir, and then add CS
2Acetone soln, reaction continue to be stirred, and adds chloroform and NaOH again, then stirs and spends the night; Add deionized water and hydrochloric acid with the noxious solvent in the volatiling reaction, filter, and thick product is dissolved in Virahol, recrystallization in normal hexane obtains required RAFT chain-transfer agent at last;
The preparation of b, PNIPAM macromolecular chain transfer agent
Get a certain amount of RAFT chain-transfer agent, NIPAM, CTA, 1,3,5-trioxane and AIBN are dissolved among the DMF, behind the logical nitrogen, place oil bath to react reaction flask; After question response is finished, open bottle stopper reaction solution is exposed to termination reaction in the air; The vacuum rotary steam desolventizing, the polymkeric substance that obtains precipitates in anhydrous diethyl ether, and triplicate obtains PNIPAM macromolecular chain transfer agent.
4. according to the described preparation method with epipolic double-response type magnetic nano-particle of claim 2, it is characterized in that PNIPAM macromolecular chain transfer agent and AzoMA reaction obtain segmented copolymer PNIPAM
m-b-PAzoMA
nA kind of concrete scheme be:
C, [6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide)-N-Hexyl methacrylate] preparation (AzoMA)
At first be with NaNO
2Be dissolved in the deionized water, resulting drips of solution be added in the hydrochloric acid soln of 4-phenetidine, continue to stir, hydrochloric acid must be excessive in this process; Then resultant azo solution is slowly added the NaOH solution of phenol and then stirring, the filemot suspended substance acidifying that obtains is also filtered, filter cake reaches 7 with the pH that deionized water washs up to filtrate, with the second alcohol and water crude product is carried out recrystallization, vacuum-drying obtains 4-hydroxyl-4 ˊ oxyethyl group nitrogen benzide (HEAB);
Then get certain amount of H EAB and 1,6-dibromo-hexane and anhydrous K
2CO
3, under the magnetic agitation state, join in the acetone soln mixture back flow reaction; After reaction is finished, heat filtering, inorganic residue is washed with acetone, collect filtrate, remove acetone soln, residual extract is poured in the sherwood oil and is precipitated, recrystallization twice in ethyl acetate, obtains the 1-Br-6-(hexane (BrEAB) of 4-oxyethyl group nitrogen benzide-4 ˊ-O);
With a certain amount of α-Jia Jibingxisuan and KHCO
3Join among the DMF, under the state that stirs, add BrEAB, revolve after the reaction to steam and remove organic solvent, cross silica gel column chromatography product is purified, obtain [6-(4 ˊ-methoxyl group-4-oxygen base nitrogen benzide)-N-Hexyl methacrylate] (AzoMA);
D, segmented copolymer PNIPAM
m-b-PAzoMA
nPreparation
A certain amount of AzoMA, PNIPAM macromolecular chain transfer agent, AIBN are dissolved in the dry-out benzene methyl ether, and logical nitrogen 15min reacts in 70 ℃-80 ℃ oil bath, takes out different samples at set intervals and carries out the GPC test, after question response is finished, uses CH
2Cl
2Dilute reaction solution, and in 30 ℃ of-60 ℃ of sherwood oils, precipitate, after the filtration, obtain segmented copolymer PNIPAM
m-b-PAzoMA
n
5. according to the described preparation method with epipolic double-response type magnetic nano-particle of claim 2, it is characterized in that segmented copolymer PNIPAM
m-b-PAzoMA
n, trivalent rare earth metals hydrochloride and TTA carry out coordination, obtain high molecular polymer M (III)-(PNIPAM
m-b-PAzoMA
nA kind of concrete scheme of)-TTA is:
E, with a certain amount of segmented copolymer PNIPAM
m-b-PAzoMA
nPlace tool plug bottle, respectively according to mass ratio M
3+: PNIPAM=0.07:1, mol ratio TTA:M
3+=2 usefulness transfer pipets are got quantitative MCl respectively
3Ethanolic soln and TTA ethanolic soln add the dehydrated alcohol constant volume at last to tool plug bottle; Bottle put under the room temperature react 48h, handle with DMF dialysis (MWCO, 10000), vacuum-drying 24h under 40 ° of C, sub-polymkeric substance M (III)-(PNIPAM secures satisfactory grades
m-b-PAzoMA
n)-TTA.
6. according to the described preparation method with epipolic double-response type magnetic nano-particle of claim 5, it is characterized in that described trivalent rare earth metals hydrochloride is EuCl
3, TbCl
3, SmCl
3Or ErCl
3
7. according to the described preparation method with epipolic double-response type magnetic nano-particle of claim 2, it is characterized in that high molecular polymer M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA modifies Fe by esterification
3O
4The surface of nano particle obtains final product Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
nA kind of concrete scheme of)-TTA is:
F, Fe
3O
4The preparation of nanoparticle
With FeCl
36H
2O and FeSO
47H
2O is dissolved in the deionized water, under the atmosphere of nitrogen reaction flask is placed water-bath, is heated to 70 ℃ gradually, violent stirring, and slow adding massfraction is 25% ammoniacal liquor 30ml when temperature is raised to 65 ℃, reaction solution is immediately by the orange black that becomes; The throw out of black is at 85 ℃ of following slaking 40min, and with a large amount of deionized water wash for several times, magnetic separates; At last throw out is dispersed in the ethanol, the washing several, magnetic separates; The product that obtains is put into dry 12h in the vacuum drying oven, obtains Fe
3O
4Nanoparticle;
G, Fe
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
nThe preparation of)-TTA
With a certain amount of Fe
3O
4Nanoparticle is dissolved in the dry DMF, and ultrasonic 15min adds M (III)-(PNIPAM of a certain amount of ratio then
m-b-PAzoMA
n)-TTA and EDCHCl and DMAP place 80 ℃ oil bath to react 24h reaction flask, and magnetic separates, and constantly wash with excessive methyl alcohol and remove unreacted polymkeric substance, behind the dry 12h, obtain final product Fe in 40 ℃ the vacuum drying oven
3O
4@M (III)-(PNIPAM
m-b-PAzoMA
n)-TTA.
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| CN108299591A (en) * | 2018-01-17 | 2018-07-20 | 常州大学 | A kind of preparation method of n-isopropyl acrylamide copolymer of the side chain containing azo pyridine |
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