CN1298791C - Superparamagnetic Fe3O4 nanometer particle with synthetic polymer modification from one-step method - Google Patents
Superparamagnetic Fe3O4 nanometer particle with synthetic polymer modification from one-step method Download PDFInfo
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- CN1298791C CN1298791C CNB2005100169928A CN200510016992A CN1298791C CN 1298791 C CN1298791 C CN 1298791C CN B2005100169928 A CNB2005100169928 A CN B2005100169928A CN 200510016992 A CN200510016992 A CN 200510016992A CN 1298791 C CN1298791 C CN 1298791C
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Abstract
The present invention relates to a superparamagnetic Fe3O4 nanoparticles modified by synthetic polymers by a one-step method, which belongs to the technical field of preparing magnetic nanometer materials. The present invention has the synthetic method that polymer monomers and bivalent ferric salt are added into oxygen-free distilled water according to the molar ratio of 1 to 20:1 and stirred under the protection of nitrogen; then the mixture is stirred at 75 to 100 DEG C under the protection of nitrogen, the mixed solution of peroxydisulfate and alkali is added into the mixture by dropping, heating is stopped after dropping, and further reaction is carried out for 30 to 60 minutes to obtain magnetic nanoparticle sol clad with black polymers; the concentration of the polymer monomers in the final reaction system is from 0.05 to 0.3 M, and the concentration of the bivalent ferric salt in the final reaction system is from 0.005 to 0.05 M. The particle size of the magnetic nanoparticles prepared by the present invention is 20 nm, the dispersion is low, the magnetic nanoparticles can be stably dispersed in water, ethanol and other solvents, and the magnetic nanoparticles have high practical application value on multi-aspect. The nanoparticle has simple method, little time consumption, high yield and no toxic pollutant, and is suitable for industrial production.
Description
Technical field
The invention belongs to the preparation field of magnetic Nano material, particularly a kind of preparation method of polymkeric substance-inorganic nano composite material is specifically related to the super paramagnetic Fe that a kind of soluble polymer of size distribution homogeneous is modified
3O
4Nanometer particle process method.
Background technology
Because and the corresponding significant difference of block materials on physical properties, magnetic Nano material has become the focus of current scientific research because of importance on its scientific theory and technical widespread use value, wherein the application development in biological association area is particularly rapid, comprise nuclear magnetic resonance (MRI), drug delivery, aspects such as the diagnosis of biological sharp separation technology and clinical diagnosis and treatment, particularly cancer and treatment.Require in above-mentioned biological association area that the magnetic nano-particle particle diameter is suitable (can be easy to enter in the most cell less than 50nm, can pass through blood vessel less than 20nm), and narrow distribution, surface-area is big or active group arranged, can be at liquid media stable existence in the water (because human body weight 98% mainly is water) particularly, and must be super paramagnetic mostly.In satisfactory magneticsubstance, ferriferous oxide (comprises Fe
3O
4And γ-Fe
2O
3) be widely used with its satisfactory stability.For reach the requirement that ferriferous oxide is used in biological association area, guarantee its stable existence and make its functionalisation of surfaces very efficient ways be exactly shell in its surface bag one deck particular polymer.
The scheme of the magnetic nano-particle that current synthetic polymer coats mainly is divided into two big classes: 1. at the magnetic nano particle sub-surface initiated polymerization thing monomer polymerization that has prepared with 2. generate magnetic nano-particle in the polymer sol system.
1. scheme can utilize the high-quality magnetic nano-particle aftertreatment that has prepared to make the magnetic nano-particle of polymer overmold, and thickness that can the polymkeric substance that control surface coated.The synthetic technology of the magnetic nano-particle of single now dispersion particle diameter reaches its maturity, and particularly the organic phase pyrolysis technique can be prepared the magnetic nano-particle of 3～20nm of single particle size.But the strong tensio-active agent that in the process of coated polymer, needs wash-out or displacement magnetic nano particle sub-surface, thereby this causes the reunion of magnetic nano-particle or tensio-active agent not to be become key to influence the stability and the homogeneity of final product by the displacement impact polymer with magnetic nano-particle fully easily, and this process is very loaded down with trivial details consuming time simultaneously.And the organic phase pyrolysis technique is relatively harsher to the requirement of reaction conditions, and temperature is higher relatively, and uses inflammable organic solvent and expensive organic reagent in a large number.
The background technology close with the present invention be scheme 2., mainly be in the system that polymkeric substance exists, to pass through Fe in as the polyelectrolyte system
2+And Fe
3+Method such as co-precipitation or thermolysis makes, its advantage is can generate the back at magnetic nano-particle to be aggregated the thing coating at once, do not spend wash-out or permutation table surface-active agent, but the difficult control of its size of particles that obtains, coprecipitation method particularly, generally all synthetic under high pH condition, a large amount of positively charged ions is together with the active group of magnetic nano-particle competition polymkeric substance, thereby causing magnetic nano-particle can not be aggregated thing coats fully, high molecular weight polymers colloidal sol viscosity is big simultaneously, the easy tied up in knots of its long-chain causes " reunion " on the another kind of meaning of magnetic nano-particle, thereby has influenced further application.
Summary of the invention
The technical problem to be solved in the present invention is to overcome disadvantages of background technology, adopt single stage method to synthesize simple, green, magnetic nano-particle cheap, that be suitable for industrial polymer overmold, make the particle diameter d＜25nm of magnetic nano-particle, have actual application value.
The present invention is precursor with the polymer monomer that has carboxyl by the salt that thermokinetics ion-exchange or solion exchange form with ferrous ion by the colloidal sol synthetic technology of improvement; with peroxydisulfate initiated polymerization thing monomer polymerization, peroxydisulfate is with a certain proportion of Fe simultaneously under nitrogen protection and constant temperature stirring
2+Be oxidized to Fe
3+, Fe after adding a small amount of alkali lye
2+And Fe
3+Form Fe
3O
4, polymerization limit, limit generates nanoparticle.
The concrete grammar of the magnetic nano-particle that synthetic polymer coats is as follows:
Get polymer monomer and divalent iron salt with mol ratio 1～20: 1 adds and fills in the reaction vessel of anaerobic distilled water, stirs under nitrogen protection 10～60 minutes; Under nitrogen protection is stirred in 75～100 ℃ then, in reaction vessel, drip the mixing solutions of peroxydisulfate and alkali, dropwise and stop heating, continue reaction 30～60 minutes, obtain the magnetic nano-particle colloidal sol that black polymer coats; Wherein the mol ratio of peroxydisulfate and divalent iron salt is 0.5～1.5: 2, and the mol ratio of alkali and polymer monomer is 0.5～2: 1; The concentration of polymer monomer is 0.05～0.3M in the end reaction system, and the concentration of divalent iron salt is 0.005～0.05M.
When the reaction system final pH greater than 7.5 the time, gained colloidal sol may settle down, and still can get stable black colloidal sol after being washed to neutrality.
Above-mentioned anaerobic distilled water was made by the logical nitrogen of distilled water in 30 minutes.
Preparation process of the present invention is a limit initiated polymerization thing monomer polymerization, and the limit generates Fe
3O
4Nanoparticle, two processes are carried out simultaneously.
In the method for the present invention, said polymer monomer is vinylformic acid, methacrylic acid or acrylamide; Divalent iron salt is iron protochloride, Iron nitrate, ferrous sulfate, Iron diacetate or ferrous ammonium phosphate; Peroxydisulfate is Sodium persulfate, Potassium Persulfate or peroxy-disulfuric acid ammonia; Alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide or ammoniacal liquor.
Gained black colloidal sol can be by centrifugation, washing, redispersion 1～2 time, after some ions on surface, unnecessary polymkeric substance and other impurity removed, ultra-sonic dispersion or just shake up to be scattered in water, ethanol and some other polar solvents and can get the black stable sols further can get clear sol transparent, homogeneous after the dilution with colloidal sol.Gained colloidal sol can stably stored 1～3 month and do not have obvious sediment to produce.
The present invention goes out the magnetic nano-particle of polymer overmold by the colloidal sol synthetic technology one-step synthesis of improvement, the particle diameter of the magnetic nano-particle of this polymer overmold after polymer overmold also just has only about 20nm, and disperse narrower, can be very stable be dispersed in water, ethanol and some other polar solvents.This method is simply direct, used reactant species is few and be easy to get, productive rate height (＞80%) is low for equipment requirements, consuming time few, temperature of reaction relatively low (require with respect to the organic phase pyrolysis technique 200-400 ℃), reaction system is a water, do not use any organic solvent, tensio-active agent and inflammable and explosive reagent, also can be synthetic under condition near neutral (pH of synthetic system between the 5.5-12 can), generate environmental protection without any the material of poisonous and contaminative.Therefore, the present invention is suitable for industrial production, and the magnetic nano-particle that coats of resulting polymers is in ferrofluid seal, magnetic ink powder, bio-sensing, bioseparation technology, clinical diagnosis with treat the diagnosis of cancer particularly and there is actual using value aspect such as treatment.In addition, because Fe
3O
4Particularly there is very strong absorption the ultraviolet region in the ultraviolet-visible district, therefore can be used for uvioresistant optics coating.
Description of drawings
Fig. 1: the transmission electron microscope photo of the magnetic nano-particle of polymer overmold;
Fig. 2: the stereoscan photograph of the magnetic nano-particle of polymer overmold;
Fig. 3: the liquid uv atlas of the magnetic nano-particle dilute solution of polymer overmold (absorption intensity graphic representation);
Fig. 4: the X-ray diffraction spectrogram of the magnetic nano-particle powder of polymer overmold;
Fig. 5: the susceptibility of the magnetic nano-particle powder of polymer overmold varies with temperature curve;
Fig. 6: when temperature is 4k the magnetic nano-particle powder of polymer overmold magnetic hysteresis loop.
Embodiment
Below in conjunction with embodiment the present invention is further set forth.
Embodiment 1:
2.5g vinylformic acid and the adding of 1.38g Iron dichloride tetrahydrate are filled in the reaction vessel of 50ml anaerobic distilled water, under nitrogen protection, slowly stirred 30 minutes.Constant temperature is powerful under the nitrogen protection in 85 ℃ of intervals then stirs, and dropwise adds the mixing solutions that 200ml contains 0.338g Potassium Persulfate and 1.8g sodium hydroxide in 4 hours in reaction vessel.Continue then to react to stop simultaneously in 30 minutes heating and naturally cool to room temperature.Centrifugation, washing, centrifugal again, can get black precipitate, the vacuum drying slim and graceful black powder of normal temperature can get stable sols and black precipitate is scattered in again in the mixing solutions of second alcohol and water, but prolonged storage.
The magnetic nano-particle of polymer overmold of preparation has been carried out the sign of some structures and performance.The transmission electron microscope of the magnetic nano-particle of polymer overmold characterizes as shown in Figure 1, the high resolution scanning electromicroscopic photograph of the magnetic nano-particle of polymer overmold as shown in Figure 2, particle diameter by Fig. 1 and Fig. 2 can be determined, the particle diameter of inorganic nuclear is 20nm, the shell mean thickness of polymkeric substance is about 5nm, and does not obviously reunite.Fig. 3 has provided the liquid of magnetic nano-particle dilute solution of polymer overmold in the absorbance curves of ultraviolet-visible optical band, shows that the light to the ultraviolet region has good absorption.As shown in Figure 4, the composition of the inorganic core of the magnetic nano-particle powder of polymer overmold can be defined as Fe by its powder x-ray diffraction spectrogram
3O
4, and diffraction peak has obvious broadening, shows that its particle is very little, is nano level.The sign of the magnetic of the magnetic nano-particle of polymer overmold such as Fig. 5.Fig. 6 provided polymer overmold when temperature is 4k the magnetic nano-particle powder magnetic hysteresis loop.Fig. 5 and Fig. 6 can determine that the magnetic nano-particle of polymer overmold is super paramagnetic.Simultaneously the gained sample dispersion being stirred 12h in the hydrochloric acid of 1M can dissolve it fully, does not have the block of coated polymer then very easily to be dissolved in the hydrochloric acid of 1M, illustrates that magnetic nano-particle is aggregated thing and coats fully.
Embodiment 2:
2.5g vinylformic acid and the adding of 0.3452g Iron dichloride tetrahydrate are filled in the reaction vessel of 50ml anaerobic distilled water, under nitrogen protection, slowly stirred 30 minutes.Constant temperature is powerful under the nitrogen protection in 85 ℃ of intervals then stirs, and dropwise adds the mixing solutions that 200ml contains 0.1688g Potassium Persulfate and 1.8g sodium hydroxide in 3 hours in reaction vessel.Continue then to react to stop simultaneously in 30 minutes heating and naturally cool to room temperature.Centrifugation, washing, centrifugal again, can get black precipitate, the vacuum drying slim and graceful black powder of normal temperature can get stable sols and black precipitate is scattered in again in the mixing solutions of second alcohol and water, but prolonged storage, particle diameter ratio embodiment 1 preparation little.
Embodiment 3:
5.0g vinylformic acid and the adding of 0.6903g Iron dichloride tetrahydrate are filled in the reaction vessel of 50ml anaerobic distilled water, under nitrogen protection, slowly stirred 30 minutes.Constant temperature is powerful under the nitrogen protection in 85 ℃ of intervals then stirs, and dropwise adds the mixing solutions that 200ml contains 0.253g Potassium Persulfate and 2.63g sodium hydroxide in 4 hours in reaction vessel.Continue then to react to stop simultaneously in 30 minutes heating and naturally cool to room temperature.Centrifugation, washing, centrifugal again, can get black precipitate, the vacuum drying slim and graceful black powder of normal temperature can get stable sols and black precipitate is scattered in again in the mixing solutions of second alcohol and water, but prolonged storage.
Embodiment 4:
Experimental technique just with 2.96g methacrylic acid substitution 2.5g vinylformic acid, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally with embodiment 2, and can prolonged storage.
Embodiment 5:
Experimental technique just replaces 2.5g vinylformic acid with the 2.468g acrylamide with embodiment 2, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally, and can prolonged storage.
Embodiment 6:
Experimental technique just replaces the 0.253g Potassium Persulfate with 0.2136g peroxy-disulfuric acid ammonia with embodiment 2, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally, and can prolonged storage.
Embodiment 7:
Experimental technique just replaces the 0.253g Potassium Persulfate with the 0.2231g Sodium persulfate with embodiment 2, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally, and can prolonged storage.
Embodiment 8:
Experimental technique just replaces the 0.3452g Iron dichloride tetrahydrate with the 0.4827g ferrous sulfate with embodiment 2, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally, and can prolonged storage.
Embodiment 9:
Experimental technique just with the ferrous replacement of 0.4998g six nitric hydrates 0.3452g Iron dichloride tetrahydrate, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally with embodiment 2, and can prolonged storage.
Embodiment 10:
Experimental technique just replaces the 0.3452g Iron dichloride tetrahydrate with 0.4270g four hydration Iron diacetates with embodiment 2, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally, and can prolonged storage.
Embodiment 11:
Experimental technique just replaces 1.8g sodium hydroxide with 2.52g potassium hydroxide with embodiment 2, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally, and can prolonged storage.
Embodiment 12:
Experimental technique just replaces 1.8g sodium hydroxide with 1.89g one hydronium(ion) oxidation lithium with embodiment 2, obtains the slim and graceful black powder and the stable sol of the magnetic nano-particle of polymer overmold equally, and can prolonged storage.
Embodiment 13:
2.5g vinylformic acid and the adding of 0.693g Iron dichloride tetrahydrate are filled in the reaction vessel of 100ml anaerobic distilled water, under nitrogen protection, slowly stirred 30 minutes.Constant temperature is powerful under the nitrogen protection in 95 ℃ of intervals then stirs; speed with 3 of per minutes dropwise adds the mixing solutions that 75ml contains 0.169g Potassium Persulfate and 1.0g sodium hydroxide in reaction vessel; reaction continues 5-6 hour, and the pH of end reaction system is 5.Continue then to react to stop simultaneously in 30 minutes heating and naturally cool to room temperature.Centrifugation, washing, centrifugal again, can get black precipitate, room temperature vacuum-drying obtains slim and graceful black powder, can get stable sols and black precipitate is scattered in again in the mixing solutions of second alcohol and water, but prolonged storage.
Embodiment 14:
1g vinylformic acid and the adding of 0.199g Iron dichloride tetrahydrate are filled in the reaction vessel of 20ml anaerobic distilled water, under nitrogen protection, slowly stirred 30 minutes.Constant temperature is powerful under the nitrogen protection in 95 ℃ of intervals then stirs, and dropwise adds the mixing solutions that 200ml contains 0.22g Potassium Persulfate and 0.8g sodium hydroxide with the speed of 3 of per minutes in reaction vessel, and reaction continues 4 hours.Continue then to react to stop simultaneously in 30 minutes heating and naturally cool to room temperature.Centrifugation, washing, centrifugal again, can get black precipitate, room temperature vacuum-drying obtains slim and graceful black powder, can get stable sols and black precipitate is scattered in again in the mixing solutions of second alcohol and water, but prolonged storage.
Embodiment 15:
0.36g vinylformic acid and the adding of 0.994g Iron dichloride tetrahydrate are filled in the reaction vessel of 50ml anaerobic distilled water, under nitrogen protection, slowly stirred 30 minutes.Constant temperature is powerful under the nitrogen protection in 95 ℃ of intervals then stirs, and dropwise adds the mixing solutions that 200ml contains 0.3375g Potassium Persulfate and 1.6g sodium hydroxide with the speed of 3 of per minutes in reaction vessel, and reaction continues 4 hours.Continue then to react to stop simultaneously in 30 minutes heating and naturally cool to room temperature.Centrifugation, washing, centrifugal again, can get black precipitate, room temperature vacuum-drying obtains slim and graceful black powder, can get stable sols and black precipitate is scattered in again in the mixing solutions of second alcohol and water, but prolonged storage.
Embodiment 16:
The solvent of the magnetic nano-particle that used dispersed polymeres coats in the foregoing description can be the mixing solutions of water or ethanol or water and any ratio of ethanol, but the shelf lives of colloidal sol is not quite similar according to the difference of the ratio of second alcohol and water.
With embodiment 1 is example, and when being spread in the dehydrated alcohol then except that water purification, gained colloidal sol can only be stored about 30 hours; And only be spread in water, when perhaps the ratio that ethanol accounts in water and the alcoholic acid mixing solutions is very low, also can stored for several weeks even longer, but sedimentation phenomenon appears in the upper strata, be the phenomenon that the colloidal particle of colloidal sol sinks because of action of gravity, upper solution becomes achromaticity and clarification.
Have only when water in mixing solutions shared volume percent 33%～67% interval in the time, the colloidal sol of the magnetic nano-particle that resulting polymers coats could store at least one moon and not have sedimentation.
Claims (3)
1, a kind of super paramagnetic Fe of single stage method synthetic polymer modification
3O
4The method of nanoparticle, it is characterized in that, get polymer monomer and divalent iron salt with mol ratio 1～20: 1 adds and fills in the reaction vessel of anaerobic distilled water, stirs under nitrogen protection 10～60 minutes, and said polymer monomer is vinylformic acid, methacrylic acid or acrylamide; Under nitrogen protection is stirred in 75～100 ℃ then, in reaction vessel, drip the mixing solutions of peroxydisulfate and alkali, dropwise and stop heating, continue reaction 30～60 minutes, obtain the magnetic nano-particle colloidal sol that black polymer coats; Wherein the mol ratio of peroxydisulfate and divalent iron salt is 0.5～1.5: 2, and the mol ratio of alkali and polymer monomer is 0.5～2: 1; The concentration of polymer monomer is 0.05～0.3M in the end reaction system, and the concentration of divalent iron salt is 0.005～0.05M.
2, according to the super paramagnetic Fe of the described single stage method synthetic polymer modification of claim 1
3O
4The method of nanoparticle is characterized in that, said divalent iron salt is iron protochloride, Iron nitrate, ferrous sulfate, Iron diacetate or ferrous ammonium phosphate; Said peroxydisulfate is Sodium persulfate, Potassium Persulfate or peroxy-disulfuric acid ammonia; Said alkali is lithium hydroxide, sodium hydroxide, potassium hydroxide or ammoniacal liquor.
3, according to the super paramagnetic Fe of claim 1 or 2 described single stage method synthetic polymer modifications
3O
4The method of nanoparticle, it is characterized in that, saidly obtain the magnetic nano-particle colloidal sol that black polymer coats, after centrifugation, washing, redispersion 1～2 time, ultra-sonic dispersion or shake up is scattered in water or the alcohol solvent, obtains transparent clear sol behind the redilution.
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| US8092705B2 (en) | 2007-05-18 | 2012-01-10 | Beijing Dingguochangsheng Biotech, Co. Ltd. | Simple method for introducing magnetic particles into a polymer |
| CN102502877B (en) * | 2011-10-18 | 2014-06-25 | 南开大学 | Simple method for synthesizing porous magnetic ferroferric oxide (Fe3O4) microspheres |
| CN107502099B (en) * | 2017-09-18 | 2019-07-23 | 山西大学 | A kind of magnetically attractive nano-waterborne coating and its preparation method and application |
| CN115197380B (en) * | 2021-12-29 | 2023-11-21 | 北京迈佳致和科技有限公司 | Preparation method and application of magnetic beads for nucleic acid fragment sorting |
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