CN1737956A - Magnetic Nano material - Google Patents
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- CN1737956A CN1737956A CN 200410058599 CN200410058599A CN1737956A CN 1737956 A CN1737956 A CN 1737956A CN 200410058599 CN200410058599 CN 200410058599 CN 200410058599 A CN200410058599 A CN 200410058599A CN 1737956 A CN1737956 A CN 1737956A
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Abstract
The present invention relates to a class magnetic nanoparticle material (magnetic fluid), they are made up of nano level magnetic metal oxide particle and the polymer that is wrapped in its outer monolayer, are characterized in that prepared magnetic fluid has very high stability.
Description
Invention field
The present invention relates to a class magnetic nanoparticle material (magnetic fluid), they are made up of nano level magnetic metal oxide particle and the polymer that is wrapped in its outer monolayer, are characterized in that prepared magnetic fluid has very high stability.
Background technology
Magnetic fluid is the magnetic nanoparticle material that is scattered in the carrier fluid, and magnetic fluid does not have magnetic attraction when static state, do the time spent when externally-applied magnetic field and then show magnetic, and after removing externally-applied magnetic field, the magnetic of its particle disappears again.Because the ferromagnetism of the existing solid magnetic material of this colloidal liquid, the flowability that liquid is arranged again, and the special nature that do not had of many other solid magnetic material and liquid substances, magnetic fluid is widely used in fields such as the immobilization, biochip technology, sealing, heat conduction, information storage, safe coding of the separating of separation, cell, virus and bacterium, magnetic targeted drug controlled release carrier, NMR (Nuclear Magnetic Resonance) imaging, the enzyme of clinical diagnosis, immunoassay, magnetic fluid thermotherapy, biochemical substances (antigen, antibody, protein, nucleic acid etc.).
The preparation method of magnetic fluid has: (1) grinding method: promptly magnetic material and activating agent, carrier fluid are milled into superfine particle together, with centrifugal process or magnetic separation method bulky grain are separated then, thereby obtain required magnetic fluid.This method is the most direct method, but is difficult to obtain the magnetic fluid of the following particle diameter of 300nm, and another shortcoming of the method is that energy consuming ratio is bigger.(2) slaine (being total to) precipitation method: iron (III) salt, iron (II) salt, cobalt (III) salt, nickel (II) salt etc. produce magnetic oxide nanoparticles under alkali condition, produce Fe as co-precipitation under molysite and the ferrous salt alkali condition
3O
4Magnetic nanoparticle adds dispersant and makes it be adsorbed in magnetic-particle surface and be scattered in and obtain magnetic fluid in the carrier fluid.This method can obtain the magnetic fluid than granule, and cost is lower.(3) carbonyls of thermal decomposition method: Fe, Co or Ni such as Co
2(CO)
8, Fe (CO)
5Deng in organic solvent heating and decomposition in the presence of the dispersant is being arranged, obtaining dispersant stable free metal nanoparticle, obtaining magnetic fluid again.(4) evaporation: at following highly purified magnetic material heating evaporation of vacuum condition, the particulate that is evaporated runs into the following ground liquid film after coagulation of being made up of dispersant and carrier fluid, and liquid film and magnetic particle move to down in the ground liquid and just obtain magnetic fluid instantly.(5) reducing process: Fe, Co or Ni salt obtain nano metal particles with alkali metal or borohydride reduction in appropriate solvent, obtain magnetic fluid in the carrier fluid with being scattered in behind the dispersant parcel.In above-mentioned magnetofluid making method, the most frequently used method is slaine (being total to) precipitation method.
Can be divided into water-based magnetic fluid and oil (organic solvent) based magnetofluid according to the different magnetic fluids of carrier fluid.The oil base magnetic fluid can pass through slaine (being total to) precipitation, and co-precipitation under alkali condition forms Fe as Fe (II) and Fe (III)
3O
4Nano particle is at Fe
3O
4Nano particle coat layer of surface activating agent such as enuatrol outward and be scattered in organic solvent such as hexane in obtain the oil base magnetic fluid.The polarity part of surfactant is as the carboxyl and the Fe of oleic acid
3O
4The Fe coordination of nano grain surface, the hydrophobic long-chain of surfactant is stretched in the organic solvent.Water-based magnetic fluid can pass through slaine (being total to) precipitation, and co-precipitation under alkali condition forms Fe as Fe (II) and Fe (III)
3O
4Nano particle, Fe under acid condition
3O
4Nano grain surface has positive charge, with some anion such as ClO
4 -Form electric double layer and be scattered in the water.Or under alkali condition Fe
3O
4Nano grain surface has negative electrical charge, with some cation as (CH
3)
4N
+Form electric double layer and be scattered in the water.The pH scope of this stable existence by the magnetic fluid of electric double layer stable dispersion in water is less, even and very the electrolyte of low concentration also can make magnetic-particle build up and be precipitated out, stability is very poor.More stable water-based magnetic fluid also can coat another laminar surface activating agent by the magnetic particle outside at the stable oil base magnetic fluid of surfactant, and therefore the hydrophilic radical of this laminar surface activating agent can be scattered in the water outwardly.The stability of this kind water-based magnetic fluid is still lower, can build up as magnetic-particle when the concentration of magnetic fluid is hanged down to become big.Generally adopt water-based magnetic fluid at magnetic fluid biological, that field of medicaments is used.Therefore, the water-based magnetic fluid of exploitation good stability is the ten minutes needs.
Summary of the invention
Existing after deliberation employing polyacrylate or polymethacrylates such as polyacrylic acid glycerol monoesters or the polymethylacrylic acid monoglyceride found of the present invention, or contain random, the block of polyacrylic acid glycerol monoesters or polymethylacrylic acid monoglyceride or graft copolymer and can obtain the water-based magnetic fluid of high stability as stabilizer, the structure of copolymer can be represented with following three general formulas:
(1) formula is represented random copolymer, and A represents the construction unit of the A component of copolymer, and n represents the degree of polymerization of A component, and A can be poly-(methyl) acrylic acid or poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester; R is hydrogen or methyl; N=10-300, m=10-300.The method of synthetic available existing any synthetic random copolymer of random copolymer as radical copolymerization etc., is more prone to adopt living Radical Copolymerization;
(2) formula is represented block copolymer, and A represents the construction unit of the A component of copolymer, and n represents the degree of polymerization of A component, A
nCan be poly-(methyl) acrylic acid, poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester or poly glycol monomethyl ether; R is hydrogen or methyl; N=10-300, m=10-300.The method of synthetic available existing any synthetic segmented copolymer of block copolymer, as active free radical polymerization (comprising ATRP (ATRP), reversible addition-cracking chain transferring free-radical polymerization (RAFT) etc.), anionic polymerization etc., be more prone to adopt active free radical polymerization or anionic polymerization;
(3) formula represents to gather (methyl) acrylic acid monoglyceride grafting A copolymer.R is hydrogen or methyl; R ' is hydrogen or methyl; A represents the construction unit of graft polymers, and its degree of polymerization is x; N=10-300, m=10-300, x=10-300; A
xCan be poly-(methyl) acrylic acid, poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester or poly glycol monomethyl ether.The method of synthetic available existing any synthesising graft copolymer of graft copolymer.
The magnetic metal oxide particle magnetic fluid of the homopolymers of (methyl) acrylic acid monoglyceride or copolymer parcel can adopt direct method or indirect method preparation.Direct method is about to the water-soluble formation aqueous solution of polymer, divalent metal salt and trivalent metal salt, under agitation in this solution, add alkaline solution (as ammoniacal liquor or NaOH solution) then, the micromolecular compound in solution is gone out in dialysis and do not obtain the magnetic fluid of polymer stabilizing behind the polymer of parcel.Indirect method is to prepare micromolecule anion such as ClO earlier
4 -, Cl
-Or NO
3 -Etc. stable magnetic fluid (R.Massart, IEEE Trans.Mag., 1981, Mag-17,1247), then aqueous solutions of polymers is joined in the stable magnetic fluid of micromolecule anion the micromolecular compound in solution is gone out in dialysis and do not obtain the magnetic fluid of polymer stabilizing behind the polymer of parcel.
The present invention adopts (methyl) acrylic acid monoglyceride or its homopolymers or copolymer water-based magnetic fluid as the stabilizer preparation of magnetic metal oxide nanoparticle, demonstrating is gained hydromagnetic stability height, but in the salting liquid of the pH of broad value and high concentration stable existence.
First aspect present invention relates to a kind of water-based magnetic fluid, and it comprises random, block or graft copolymer or the homopolymers and the magnetic metal oxide of polyacrylate or polymethacrylates or they.
The invention still further relates to the purposes in the preparation water-based magnetic fluid.
Further aspect of the present invention relates to the preparation method of water-based magnetic fluid, and it comprises random, the block of polyacrylate or polymethacrylates or they or graft copolymer or homopolymers are mixed with magnetic metal oxide.
According to the present invention, random, the block of polyacrylate or polymethacrylates or they or the following expression of structure of graft copolymer or homopolymers:
(1) formula is represented random copolymer, and A represents the construction unit of the A component of copolymer, and n represents the degree of polymerization of A component, and A can be poly-(methyl) acrylic acid or poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester; R is hydrogen or methyl; N=10-300, m=10-300.The method of synthetic available existing any synthetic random copolymer of random copolymer as radical copolymerization etc., is more prone to adopt living Radical Copolymerization;
(2) formula is represented block copolymer, and A represents the construction unit of the A component of copolymer, and n represents the degree of polymerization of A component, A
nCan be poly-(methyl) acrylic acid, poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester or poly glycol monomethyl ether; R is hydrogen or methyl; N=10-300, m=10-300.The method of synthetic available existing any synthetic segmented copolymer of block copolymer, as active free radical polymerization (comprising ATRP (ATRP), reversible addition-cracking chain transferring free-radical polymerization (RAFT) etc.), anionic polymerization etc., be more prone to adopt active free radical polymerization or anionic polymerization;
(3) formula represents to gather (methyl) acrylic acid monoglyceride grafting A copolymer.R is hydrogen or methyl; R ' is hydrogen or methyl; A represents the construction unit of graft polymers, and its degree of polymerization is x; N=10-300, m=10-300, x=10-300; A
xCan be poly-(methyl) acrylic acid, poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester or poly glycol monomethyl ether.The method of synthetic available existing any synthesising graft copolymer of graft copolymer.
Further, random, the block of polyacrylate or polymethacrylates or they or graft copolymer or homopolymers are preferably polyacrylic acid glycerol monoesters or polymethylacrylic acid monoglyceride, or contain random, the block or the graft copolymer of polypropylene monoglyceride or polymethylacrylic acid monoglyceride.
According to the present invention, magnetic metal oxide has been said for example in the water-based magnetic fluid of the present invention:
The mictomagnetism oxide that contains in ferromagnetic oxide, cobalt-containing magnetic oxide, nickeliferous magnetic oxide or iron, cobalt, three kinds of elements of nickel any two.
Embodiment
The following examples are used for further specifying the present invention, but it does not mean that any limitation of the invention.
The preparation of embodiment 1 acrylic acid monoglyceride-acrylic acid random copolymer (PGA-r-PAA)
Prepare acrylic acid monoglyceride-acrylic acid random copolymer (PGA-r-PAA) by ATRP: 39mg (0.27mmol) CuBr is joined in the round-bottomed flask of 50ml band arm, the turned welt rubber stopper seals, arm is connected with vacuum line with rubber tube, vacuumizes-inflated with nitrogen circulation three times.Then with the syringe 5.0g of deoxidation gas (27mmol) acrylic acid-2,2-dimethyl-1,3-dioxolane-4-methyl ester, 2.4g (19mmol) tert-butyl acrylate and 47mg (0.27mmol) N, N, N ', N "; N "-PMDETA, magnetic agitation 10min.45mg (0.27mmol) 2-bromo propionic acid A ester is added, and solution becomes light green color in the reaction bulb.Reaction bulb placed be preheating to 60 ℃ oil bath, stirring reaction 5 hours.Be cooled to room temperature, with 40ml acetone solution resulting polymers solid, flow of solution is crossed Al
2O
3(5cm * 1cm, ID), outflow liquid is concentrated into dried post through rotary evaporation, vacuumize.The sample analysis that takes a morsel, GPC result is: M
n=2.47 * 10
4, M
w/ M
n=1.29;
1H NMR result shows, polyacrylic acid-2, and 2-dimethyl-1, the unit chain link ratio of the 3-dioxolane-4-methyl ester and the polyacrylic acid tert-butyl ester is 1.19: 1.The above-mentioned gained copolymer of 2g is dissolved in the carrene of 6ml drying, add the 6ml trifluoroacetic acid, stir 3h, and then add 0.6ml water, and stirring 5h, rotary evaporation is concentrated into small size, after first 10ml water mixes again rotary evaporation be concentrated into small size, so repeat 3 times, last water dissolved dilution gets the PGA-r-PAA that concentration is about 0.14g/ml to 10ml.
The preparation of embodiment 2 methacrylic acid monoglyceride-methacrylic acids (N, TMSDMA N dimethylamine base ethyl) ester random copolymer (PGMA-r-PDMAEMA)
Prepare methacrylic acid monoglyceride-methacrylic acid (N by ATRP, TMSDMA N dimethylamine base ethyl) ester random copolymer (PGMA-r-PDMAEMA): 39mg (0.27mmol) CuBr is joined in the round-bottomed flask of 50ml band arm, the turned welt rubber stopper seals, arm is connected with vacuum line with rubber tube, vacuumizes-inflated with nitrogen circulation three times.Then with the syringe 5.4g of deoxidation gas (27mmol) methacrylic acid-2,2-dimethyl-1,3-dioxolane-4-methyl ester and 4.2g (27mmol) methacrylic acid (N, TMSDMA N dimethylamine base ethyl) ester, 7ml acetone and 47mg (0.27mmol) N, N, N ', N "; N "-PMDETA, magnetic agitation 10min.45mg (0.27mmol) 2-bromo propionic acid A ester is added, and solution becomes light green color in the reaction bulb.Reaction bulb placed be preheating to 55 ℃ oil bath, stirring reaction 12 hours.Be cooled to room temperature, with 40ml acetone solution resulting polymers, flow of solution is crossed Al
2O
3(5cm * 1cm, ID), outflow liquid is concentrated into dried post through rotary evaporation, vacuumize.The sample analysis that takes a morsel, GPC result is: M
n=2.65 * 10
4, M
w/ M
n=1.20;
1H NMR result shows, polymethylacrylic acid-2, and 2-dimethyl-1, the unit chain link ratio of 3-dioxolane-4-methyl ester and polymethylacrylic acid (N, TMSDMA N dimethylamine base ethyl) ester is 1: 0.89.The above-mentioned gained copolymer of 2g is dissolved among the 20ml THF, add 2ml 6mol/L HCl, stir 5h, rotary evaporation is concentrated into small size, after adding 10ml water and mixing again rotary evaporation be concentrated into small size, so repeat 3 times, last water dissolved dilution gets the PGMA-r-PDMAEMA that concentration is about 0.18g/ml to 10ml.
The preparation of embodiment 3 polymethylacrylic acid-polymethylacrylic acid monoglyceride block copolymer (PMA-b-PGMA)
Prepare polymethylacrylic acid-polymethylacrylic acid monoglyceride block copolymer (PMA-b-PGMA) by ATRP: 72mg (0.5mmol) CuBr is joined in the round-bottomed flask of 50ml band arm, the turned welt rubber stopper seals, arm is connected with vacuum line with rubber tube, vacuumizes-inflated with nitrogen circulation three times.Then with the syringe 5.7g of deoxidation gas (40mmol) metering system tert-butyl acrylate, 6ml acetone and 86.7mg (0.5mmol) N, N, N ', N ", N " PMDETA, magnetic agitation 10min.83.5mg (0.5mmol) 2-bromo propionic acid A ester is added, and solution becomes light green color in the reaction bulb.Reaction bulb placed be preheating to 55 ℃ oil bath, stirring reaction 10 hours.Be cooled to room temperature, with 40ml acetone solution resulting polymers, flow of solution is crossed Al
2O
3(5cm * 1cm ID), flows out liquid and is concentrated into smaller size smaller through rotary evaporation post, with 1: 1 (volume ratio) methanol aqueous solution precipitation polymers, vacuumize, gets polymethyl tert-butyl acrylate.The sample analysis that takes a morsel, GPC result is: M
n=1.19 * 10
4, M
w/ M
n=1.22, it is 84 that calculating can get the constitutional unit number.
The above-mentioned polymethyl tert-butyl acrylate that makes of 1.8g (0.15mmol), 22mg (0.15mmol) CuBr are joined in the round-bottomed flask of 100ml band arm, the turned welt rubber stopper seals, and arm is connected with vacuum line with rubber tube, vacuumize-inflated with nitrogen circulates three times.Then with the syringe 9.0g of deoxidation gas (45mmol) methacrylic acid-2,2-dimethyl-1,3-dioxolane-4-methyl ester and 5ml acetone, stirring is all dissolved polymer at a slow speed, adds 26.0mg (0.15mmol) N then, N, N ', N ", N " PMDETA, stir, solution becomes light green color in the reaction bulb.Reaction bulb placed be preheating to 55 ℃ oil bath, stirring reaction 16 hours.Be cooled to room temperature, with 60ml acetone solution resulting polymers, flow of solution is crossed Al
2O
3(5cm * 1cm ID), flows out liquid and is concentrated into smaller size smaller through rotary evaporation, the n-hexane precipitation polymers post.The sample analysis that takes a morsel, GPC result is: M
n=6.05 * 10
4, M
w/ M
n=1.39.Result in conjunction with polymethyl tert-butyl acrylate can calculate, and the construction unit number of polymethyl tert-butyl acrylate is 84 in the gained copolymer, polymethylacrylic acid-2, and 2-dimethyl-1, the construction unit number of 3-dioxolane-4-methyl ester is 243.The above-mentioned gained copolymer of 2g is dissolved in the carrene of 6ml drying, adds the 6ml trifluoroacetic acid, stir 3h.Rotary evaporation is removed most of carrene, adds 20ml 6mol/L HCl/THF (1/9, volume ratio) then, stirs, and stirs 5h under the room temperature.Rotary evaporation is concentrated into small size, after first 10ml water mixes again rotary evaporation be concentrated into small size, so repeat 3 times, last water dissolved dilution is to 10ml, concentration is about the PMA-b-PGMA of 0.16g/ml.
The preparation of embodiment 4 polyethylene glycol-acrylic acid monoglyceride block copolymers (MPEG-b-PGA)
Prepare polyethylene glycol-acrylic acid monoglyceride block copolymer (MPEG-b-PGA) by ATRP: in the 250ml round-bottomed flask, mix 10g (5mmol) dry poly glycol monomethyl ether (MPEG-OH, M
n=2000, n=45), 1.0g (10mmol) triethylamine, 70ml THF, and add a magnetic stick.Immerse in the ice-water bath, stir, get white paste.After 30 minutes, slowly drip 4.6g (20mmol) 2-bromine isobutyl acylbromide, dropwise the back and be warmed up to room temperature, stirring reaction 48 hours naturally.Rotary evaporation is removed THF, adds the water-soluble products therefrom of separating of 100ml.Then with dichloromethane extraction, each 30ml, organic facies is collected in coextraction 5 times.Use 1M HCl (30ml * 3) respectively, 1M NaOH (containing small amount of N aCl, 30ml * 3), saturated aqueous common salt (30ml * 3) washs successively, and collects organic facies, at last with anhydrous MgSO
4Dry.Remove by filter drier, rotary evaporation removes and desolvates, and the gained concentrate precipitates with absolute ether, collecting precipitation.Reprecipitation once promptly gets product.Vacuumize got the MPEG initator more than 24 hours.
The above-mentioned MPEG initator that makes of 0.65g (0.3mmol), 44mg (0.3mmol) CuBr are joined in the round-bottomed flask of 50ml band arm, the turned welt rubber stopper seals, and arm is connected with vacuum line with rubber tube, vacuumize-inflated with nitrogen circulates three times.Then with the syringe 5.6g of deoxidation gas (30mmol) acrylic acid-2,2-dimethyl-1,3-dioxolane-4-methyl ester and 3ml acetone, stirring is all dissolved polymer at a slow speed, adds 52.0mg (0.15mmol) N then, N, N ', N ", N " PMDETA, stir, solution becomes light green color in the reaction bulb.Reaction bulb placed be preheating to 55 ℃ oil bath, stirring reaction 12 hours.Be cooled to room temperature, with 30ml acetone solution resulting polymers, flow of solution is crossed Al
2O
3(5cm * 1cm ID), flows out liquid and is concentrated into smaller size smaller through rotary evaporation, the n-hexane precipitation polymers post.The sample analysis that takes a morsel, GPC result is: M
n=1.92 * 10
4, M
w/ M
n=1.30.Calculate polyacrylic acid in the copolymer-2,2-dimethyl-1, the construction unit number of 3-dioxolane-4-methyl ester is 92.The above-mentioned gained copolymer of 2.0g is dissolved among the 20ml THF, add 2ml 6mol/L HCl, stir 5h, rotary evaporation is concentrated into small size, after adding 10ml water and mixing again rotary evaporation be concentrated into small size, so repeat 3 times, last water dissolved dilution gets the MPEG-b-PGA that concentration is about 0.16g/ml to 10ml.
The preparation of embodiment 5 polymethylacrylic acid monoglyceride grafting ethylene glycol copolymers (PGMA-g-MPEG)
Prepare polymethylacrylic acid monoglyceride grafting ethylene glycol copolymer (PGMA-g-MPEG) by ATRP: in the 250ml round-bottomed flask, mix 10g (10mmol) dry poly glycol monomethyl ether (MPEG-OH, M
n=1000, n=22), 1.0g (10mmol) triethylamine, 70ml THF, and add a magnetic stick.Immerse in the ice-water bath, stir after 30 minutes, slowly drip 4.2g (40mmol) methacrylic chloride, dropwise the back and be warmed up to room temperature, stirring reaction 48 hours naturally.Rotary evaporation is removed THF, adds the water-soluble products therefrom of separating of 100ml.Then with dichloromethane extraction, each 30ml, organic facies is collected in coextraction 5 times.Use 1M HCl (30ml * 3) respectively, 1M NaOH (containing small amount of N aCl, 30ml * 3), saturated aqueous common salt (30ml * 3) washs successively, and collects organic facies, at last with anhydrous MgSO
4Dry.Remove by filter drier, rotary evaporation removes and desolvates, and the gained concentrate precipitates with absolute ether, collecting precipitation.Reprecipitation once promptly gets product.Vacuumize got metering system (poly glycol monomethyl ether) ester (MPEGMA) more than 24 hours.
72mg (0.5mmol) CuBr, 3.2g (3mmol) MPEGMA are joined in the round-bottomed flask of 50ml band arm, the turned welt rubber stopper seals, and arm is connected with vacuum line with rubber tube, vacuumize-inflated with nitrogen circulates three times.Then with the syringe 4.8g of deoxidation gas (30mmol) methacrylic acid monoglyceride, 4ml methyl alcohol and 86.7mg (0.5mmol) N, N, N ', N ", N " PMDETA, magnetic agitation 10min.50.1mg (0.3mmol) 2-bromo propionic acid A ester is added.Stirring reaction is 10 hours under the room temperature.With 40ml dissolve with methanol resulting polymers, flow of solution cross silicagel column (5cm * 1cm ID), flows out liquid and is concentrated into smaller size smaller through rotary evaporation, and using by molecular weight is that 2000 dialysis substitutes the water dialysis, PGMA-g-MPEG.GPC result is: M
n=1.86 * 10
4, M
w/ M
n=1.42.
The preparation of the embodiment grafting polyacrylic acid copolymerized things of 6 polyacrylic acid glycerol monoesters (PGA-g-PAA)
Prepare the grafting polyacrylic acid copolymerized thing of polyacrylic acid glycerol monoesters (PGA-g-PAA) by ATRP: 96mg (0.67mmol) CuBr is joined in the round-bottomed flask of 50ml band arm, the turned welt rubber stopper seals, arm is connected with vacuum line with rubber tube, vacuumizes-inflated with nitrogen circulation three times.Then with the syringe 7.7g of deoxidation gas (60mmol) tert-butyl acrylate, 4ml acetone and 225mg (1.3mmol) N, N, N ', N ", N " pentamethyl-divinyl triamine, magnetic agitation 10min.422mg (2.0mmol) 2-bromo acid hydroxyl ethyl ester is added, reacted 72 hours down at 35 ℃.With 40ml acetone solution resulting polymers, flow of solution is crossed Al
2O
3(5cm * 1cm ID), flows out liquid and is concentrated into smaller size smaller through rotary evaporation post, with 1: 1 (volume ratio) methanol aqueous solution precipitation polymers, vacuumize, gets the not brominated polyacrylic acid tert-butyl ester of end group.The sample analysis that takes a morsel, GPC result is: M
n=3.2 * 10
3, M
w/ M
n=1.25, it is 25 that calculating can get the constitutional unit number.
The polyacrylic acid tert-butyl ester that 5g (1.6mmol) is made above is dissolved among the 25ml THF, and adding 162mg (1.6mmol) triethylamine drips 1.5g (16mmol) acryloyl chloride under cryosel bath cooling, and reaction was stirred 3 hours, removes cryosel bath afterreaction and spends the night.Add about 100ml frozen water, collecting precipitation, vacuumize, the polyacrylic acid tert-butyl ester of propylene acidylate.
The polyacrylic acid tert-butyl ester of 29mg (0.2mmol) CuBr, 3.2g (1.0mmol) propylene acidylate is joined in the round-bottomed flask of 50ml band arm, the turned welt rubber stopper seals, and arm is connected with vacuum line with rubber tube, vacuumize-inflated with nitrogen circulates three times.Then with the syringe 3.9g of deoxidation gas (20mmol) acrylic acid-2,2-dimethyl-1,3-dioxolane-4-methyl ester, 3.5ml acetone and 35mg (0.2mmol) N, N, N ', N "; N "-pentamethyl-divinyl triamine slowly stirs until forming homogeneous phase solution.33mg (0.2mmol) 2-bromo propionic acid A ester is added.Be heated to 55 ° of reactions 10 hours.With 30ml acetone solution resulting polymers, flow of solution is crossed silicagel column, and (5cm * 1cm ID), flows out liquid and is concentrated into smaller size smaller through rotary evaporation.GPC result is: M
n=2.35 * 10
4, M
w/ M
n=1.45.Resulting polymers dissolves with the 30ml carrene, and rotary evaporation is to doing three times so repeatedly.Add the 20ml carrene then and make polymer dissolution, add the 20ml trifluoroacetic acid, stirred 3 hours under the room temperature, rotary evaporation is removed most of carrene.Add 20ml THF then, stir, add 2ml6mol/L HCl, stir 5h under the room temperature.Rotary evaporation removes and to desolvate, and separates with 10ml is water-soluble, and using by molecular weight is that 10000 dialysis substitutes the water dialysis, must PGA-g-PAA.
1H NMR result shows that the ratio of the chain number of PGA and PAA is 1: 1.02.
Embodiment 7 ClO
4 -The preparation of stable magnetic fluid
ClO
4 -The preparation of stable magnetic fluid: with 1.99g (10mmol) FeCl
24H
2O is dissolved in 25ml 1.0mmol/L HCl, 5.41g (20mmol) FeCl
36H
2O is dissolved in the water of 25ml deoxidation, mixes above-mentioned two solution, drips 160ml 1.5mol/L ammoniacal liquor under magnetic agitation and nitrogen protection, produces black precipitate in the solution, lasts 1 hour and dropwises, and continues to stir 24 hours.Stop to stir, hold with magnet and precipitate the supernatant liquor that inclines, wash with water 3 times.Dropwise 5 0ml2mol/L HClO then
4, stirring at room 15 minutes.Left standstill 10 minutes, clear by the last method upper strata of inclining.Dropwise 5 0ml 2mol/L HClO again
4, stirring at room 15 minutes.With centrifugal 30 minutes of reactant, the solution that inclines washed with water once after stopping to stir.Add 50ml water, stir 20min, supernatant is ClO
4 -Stable magnetic fluid.The concentration that records magnetic fluid through gravimetric method is 2.5%.
The preparation of the magnetic fluid that embodiment 8 PGA-r-PAA are stable (indirect method)
The magnetic fluid that PGA-r-PAA is stable (indirect method): get 2ml by the magnetic fluid that embodiment 7 makes, add 0.3ml by the PGA-r-PAA that embodiment 1 makes, stir, centrifugal, supernatant is the stable magnetic fluid of PGA-r-PAA.This magnetic fluid is at pH1-14,2mol/L NaCl, 2mol/L CaCl
2In stable.TEM shows that the diameter of magnetic particle is～12nm.
The preparation of the magnetic fluid that embodiment 9 PGMA-r-PDMAEMA are stable (indirect method)
The magnetic fluid that PGMA-r-PDMAEMA is stable (indirect method): get 2ml by the magnetic fluid that embodiment 7 makes, add 0.3ml by the PGMA-r-PDMAEMA that embodiment 2 makes, stir, centrifugal, supernatant is the stable magnetic fluid of PGA-r-PAA.This magnetic fluid is at pH1-7,2mol/L NaCl, 2mol/L CaCl
2In stable.TEM shows that the diameter of magnetic particle is～12nm.
Embodiment 10-13
Use the PGA-r-PAA in PMA-b-PGMA (getting), MPEG-b-PGA (getting), PGMA-g-MPEG (getting), PGA-g-PAA (getting) (consumption of copolymer is about 25mg) alternate embodiment 8 respectively, the stable magnetic fluid of preparation corresponding copolymers by embodiment 6 by embodiment 5 by embodiment 4 by embodiment 3.The magnetic fluid of the performance of gained magnetic fluid and the size of magnetic particle and embodiment 8 is similar.The size that magnetic particle is described is mainly by ClO
4 -The size decision of stable magnetic fluid.
The preparation of the magnetic fluid that embodiment 14 PGA-r-PAA are stable (direct method)
The magnetic fluid that PGA-r-PAA is stable (direct method): with the PGA-r-PAA that 0.5ml is made by embodiment 1,2ml water mixes, and adds 36.8mg (0.185mmol) FeCl
24H
2O and 100mg (0.370mmol) FeCl
36H
2O stirs and makes its dissolving, and the oxygen in the logical nitrogen conversion reaction bottle is heated to 80 ℃.Under agitation in reaction bulb, add the ammonia spirit (1.48mmol) of 0.35ml 25% then, produce black precipitate immediately.React after 2 hours, naturally cool to room temperature.Hold unnecessary precipitation with magnet, inclining supernatant liquor.With redistilled water dialysis for several times to pH near 7.Get the stable magnetic fluid of PGA-r-PAA.This magnetic fluid is at pH1-14,2mol/L NaCl, 2mol/L CaCl
2In stable.TEM shows that the diameter of magnetic particle is～10nm.
The preparation of the magnetic fluid that embodiment 15 PGMA-r-PDMAEMA are stable (direct method)
The magnetic fluid that PGMA-r-PDMAEMA is stable (direct method): with the PGMA-r-PDMAEMA that 0.5ml is made by embodiment 2,2ml water mixes, and adds 36.8mg (0.185mmol) FeCl
24H
2O and 100mg (0.370mmol) FeCl
36H
2O stirs and makes its dissolving, and the oxygen in the logical nitrogen conversion reaction bottle is heated to 80 ℃.Under agitation in reaction bulb, add the ammonia spirit (1.48mmol) of 0.35ml 25% then, produce black precipitate immediately.React after 2 hours, naturally cool to room temperature.Wash precipitation 3 times with water, add 3ml 0.01mol/L HCl then, get the stable magnetic fluid of PGMA-r-PDMAEMA.This magnetic fluid is at pH1-7,2mol/L NaCl, 2mol/L CaCl
2In stable.TEM shows that the diameter of magnetic particle is～14nm.
Claims (8)
1. water-based magnetic fluid, it comprises polyacrylic acid glycerol monoesters, polymethylacrylic acid monoglyceride, contain random, the block of random, the block of polyacrylic acid glycerol monoesters or graft copolymer or polymethylacrylic acid monoglyceride or graft copolymer as stabilizer and magnetic metal oxide.
2. magnetic fluid according to claim 1, the degree of polymerization that it is characterized in that polyacrylic acid glycerol monoesters or polymethylacrylic acid monoglyceride is 10-300.
3. magnetic fluid according to claim 1, random, the block or the graft copolymer of wherein said random, the block that contains the polyacrylic acid glycerol monoesters or graft copolymer or polymethylacrylic acid monoglyceride can be represented with following three general formulas:
(1) formula is represented random copolymer, and A represents the construction unit of the A component of copolymer, and n represents the degree of polymerization of A component, A is selected from poly-(methyl) acrylic acid or poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester; R is hydrogen or methyl; N=10-300, m=10-300;
(2) formula is represented block copolymer, and A represents the construction unit of the A component of copolymer, and n represents the degree of polymerization of A component, A
nBe selected from poly-(methyl) acrylic acid, poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester or poly glycol monomethyl ether; R is hydrogen or methyl; N=10-300, m=10-300;
(3) formula represents to gather (methyl) acrylic acid monoglyceride grafting A copolymer.R is hydrogen or methyl; R ' is hydrogen or methyl; A represents the construction unit of graft polymers, and its degree of polymerization is x; N=10-300, m=10-300, x=10-300; A
xBe selected from poly-(methyl) acrylic acid, poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester or poly glycol monomethyl ether.
4. magnetic fluid according to claim 1, wherein magnetic metal oxide is selected from the mictomagnetism oxide that contains in ferromagnetic oxide, cobalt-containing magnetic oxide, nickeliferous magnetic oxide or iron, cobalt, three kinds of elements of nickel any two.
5. random, the block of polyacrylate glycerine list or polymethylacrylic acid monoglyceride or they or graft copolymer or the purposes of homopolymers in the preparation water-based magnetic fluid.
6. purposes according to claim 5, the degree of polymerization that it is characterized in that polyacrylic acid glycerol monoesters or polymethylacrylic acid monoglyceride is 10-300.
7. purposes according to claim 5, random, the block or the graft copolymer of wherein said random, the block that contains the polyacrylic acid glycerol monoesters or graft copolymer or polymethylacrylic acid monoglyceride can be represented with following three general formulas:
(1) formula is represented random copolymer, and A represents the construction unit of the A component of copolymer, and n represents the degree of polymerization of A component, A is selected from poly-(methyl) acrylic acid or poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester; R is hydrogen or methyl; N=10-300, m=10-300;
(2) formula is represented block copolymer, and A represents the construction unit of the A component of copolymer, and n represents the degree of polymerization of A component, A
nBe selected from poly-(methyl) acrylic acid, poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester or poly glycol monomethyl ether; R is hydrogen or methyl; N=10-300, m=10-300;
(3) formula represents to gather (methyl) acrylic acid monoglyceride grafting A copolymer.R is hydrogen or methyl; R ' is hydrogen or methyl; A represents the construction unit of graft polymers, and its degree of polymerization is x; N=10-300, m=10-300, x=10-300; A
xBe selected from poly-(methyl) acrylic acid, poly-(methyl) acrylic acid (N, TMSDMA N dimethylamine base ethyl) ester or poly glycol monomethyl ether.
8. purposes according to claim 5, wherein magnetic metal oxide is selected from the mictomagnetism oxide that contains in ferromagnetic oxide, cobalt-containing magnetic oxide, nickeliferous magnetic oxide or iron, cobalt, three kinds of elements of nickel any two.
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