CN101343370A - Water dispersible magnetic polymer microsphere and preparing method - Google Patents
Water dispersible magnetic polymer microsphere and preparing method Download PDFInfo
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Abstract
The invention discloses water dispersible magnetic polymer microsphere and the preparation method. The water dispersible magnetic polymer microsphere is a compound formed by inorganic superparamagnetic center and high molecular polymer together, wherein, the inner layer (nucleus layer) is polymerized by the copolymer of the monomer of the polymer which can generate the magnetic center at the home position and the hydrophobic monomer through first-step soap-free emulsion; the outer layer is polymerized by the copolymer of hydrophilic monomer and hydrophobic monomer through second-step soap-free emulsion; the polymers of the inner layer and the outer layer are randomly copolymerized, and is obtained through adopting the polymerization of two-step soap-free emulsion and the original position method. The water dispersible magnetic high polymer microsphere and the preparation method has the advantages that the implementation is simple, the water dispersible magnetic polymer microsphere is economical and practical, not only the defects of the ordinary polymerizing method and activation swelling method of the soap-free emulsion are overcome,, and simultaneously the advantages of the both methods are combined, the particle diameters of the prepared water dispersible magnetic polymer microspheres are relatively uniformly distributed, the water dispersible magnetic polymer microsphere has good water dispersibility and biological compatibility, the magnetic difference is little, and the magnetic content is larger.
Description
Technical field
The present invention relates to polymeric material field, particularly a kind of water dispersible magnetic high polymer microsphere and preparation method thereof.
Background technology
Magnetic macromolecular microsphere is meant by proper method inorganic magnetic nanoparticle and high molecular polymer is carried out the compound spherical functional materials that obtains, can be widely used in biochemical fields such as immobilized enzyme, cellular segregation, targeted drug, environmental monitoring, also can be used as the organic and inorganic compounded mix, be applied to fields such as magnetic plastics, magnetic rubber and magnetic coating.Magnetic macromolecular microsphere can be divided into 3 classes by structure, and a class is formed nuclear by magneticsubstance, and polymkeric substance is formed shell, and is promptly hud typed; Another kind of be with polymkeric substance as nuclear, magneticsubstance is as shell, i.e. core-shell type; Also having a kind of is that ectonexine is a polymkeric substance, and the centre is the multilayer microballoon of magneticsubstance.At present, more about the research of hud typed magnetic macromolecular microsphere, with regard to its preparation method, mainly contain blend entrapping method, monomer polymerization method and activation swelling method.(1) the blend entrapping method be dispersed in the magnetic ultrafine particle natural or synthetic macromolecule solution in, make polymer be coated on the magnetic-particle surface by means such as crosslinked, flocculation, atomizing, dehydrations, form the magnetic macromolecular microsphere of nucleocapsid structure.But, adopt the magnetic macromolecular microsphere size of this method preparation to be difficult to control, broad particle distribution, out-of-shape, different microballoon magnetic-particle content are also inconsistent, and the strong and weak difference of microballoon magnetic is very big, and the magnetic core easily contacts with extraneous, and magnetic is revealed easily.(2) monomer polymerization method is in the presence of magnetic particle and monomer, adds the core-shell type magnetic macromolecular microsphere that initiator, stablizer etc. are polymerized.But, the microballoon magnetic that adopts the preparation of this method generally a little less than, chemistry and mechanical stability are also relatively poor, are separated easily in the polymerization process, cause synthetic microballoon magnetic-particle content low, also heterogeneity distributes.(3) the activation swelling method is a kind of effective ways that prepare the monodisperse superparamagnetic polymer microsphere, and Zhi Bei magnetic macromolecular microsphere does not have proper nucleocapsid structure in fact by this method, but a kind of structure of mixed type.But the preparation process of this method is very complicated, so the price of products obtained therefrom is expensive especially.
In sum, because the method that existing preparation has a magnetic macromolecular microsphere of nucleocapsid structure all has deficiency to a certain extent, thereby it is comparatively simple to invent a kind of process, the cheap relatively and prepared magnetic macromolecular microsphere size distribution homogeneous of cost, size is controlled easily and magnetic content is higher, and the method for preparing magnetic high molecular micro ball that magnetic responsiveness is stronger just seems very important.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, the water dispersible magnetic high polymer microsphere that a kind of preparation technology is simple, cost is lower, size distribution is even, magnetic content is higher and magnetic responsiveness is stronger is provided.
Another object of the present invention is to provide a kind of preparation method of above-mentioned water dispersible magnetic high polymer microsphere.
Purpose of the present invention is achieved through the following technical solutions:
A kind of water dispersible magnetic high polymer microsphere, by inorganic superparamagnetism center and the common mixture of forming of high molecular polymer, internal layer (stratum nucleare) but produce the polymer monomer at magnetic center and the multipolymer of hydrophobic monomer for having original position, form by the first step emulsifier-free emulsion polymerization; Outer (shell) is the multipolymer of hydrophilic monomer and hydrophobic monomer, formed by the second step emulsifier-free emulsion polymerization; Between internal layer and the outer field polymkeric substance is random copolymerization.
Described hydrophilic monomer is meant to have water-soluble or wetting ability by this monomer institute synthetic polymkeric substance, the small molecule monomer, propylene aldehydes monomer and the polyoxyethylene esters of acrylic acid macromonomer that contain hydrophilic functional groups (as hydroxyl or amino), preferred Hydroxyethyl acrylate (HEA) or poly glycol monomethyl ether acrylate (200) are (mPEG-methacrylate).
Described hydrophobic monomer is aromatic series alkene class or aliphatics unsaturated ester class; Optimization styrene (St) or methacrylic ester (MMA).
It is tert-butyl acrylate or the vinyl monomer that contains tert-butyl ester base that but described original position produces the polymer monomer at magnetic center.
Described inorganic superparamagnetic material is for having paramagnetic inorganic metal or its oxide compound, as iron (Fe) simple substance, ferrocobalt, Z 250 (Fe
3O
4) or γ-ferric oxide (γ-Fe
2O
3).
The particle diameter of described water dispersible magnetic high polymer microsphere is 400～1500nm, and magnetic content is 3～35%, and saturation magnetization is 1.0～15.0emu/g, and superparamagnetism center (being magnetic particle) be uniformly dispersed in polymer microsphere inside, strong to magnetic responsiveness; The polymer microsphere monodispersity well also can well be dispersed in the water again.
The preparation method of above-mentioned water dispersible magnetic high polymer microsphere adopts two step emulsifier-free emulsion polymerization and in-situ methods, comprises the steps:
(1) but make by the first step emulsifier-free emulsion polymerization and to have the polymkeric substance " nuclear " that original position produces the magnetic center, i.e. the preparation of stratum nucleare: the initiator of adding 1 mass parts and the deionized water of 1000～1500 mass parts in reaction vessel earlier; The polymer monomer that simultaneously but the original position of the linking agent of the hydrophobic monomer of 3.3～50 mass parts, 3.3～10 mass parts and 10～100 mass parts is produced the magnetic center mixes and obtains mix monomer; In atmosphere of inert gases with under stirring, mix monomer is added in the above-mentioned reaction vessel that initiator and deionized water be housed, temperature of reaction is 50～90 ℃, the reaction times is 6～24 hours, obtains the seed polymer emulsion;
(2) by the final polymer microballoon that forms of the second step emulsifier-free emulsion polymerization: in above-mentioned seed polymer emulsion, add the initiator of 0.2～0.4 mass parts and the deionized water of 300～500 mass parts with nucleocapsid structure, temperature is raised to 50～90 ℃, add the shell mix monomer that the linking agent by the shell hydrophobic monomer of the shell hydrophilic monomer of 20～200 mass parts, 30～240 mass parts and 10～40 mass parts mixes then in atmosphere of inert gases with under stirring, reaction times is 6～24 hours, obtains polymer emulsion;
(3) in-situ preparing high molecule magnetic microsphere: polymer emulsion pre-freeze after centrifugal treating that step 2 is made, carry out vacuum-drying then, adopt the mixing solutions of trifluoroacetic acid and methylene dichloride to disperse hydrolysis again, the gained hydrolysate is removed small molecular weight impurity through dialysis earlier, again dialyzate is mixed with volume ratio 1: 0.5～2 with the ferrous ion compound solution and stir, and to regulate pH value with alkali be 7～9, makes and carboxyl bonded ferrous iron precipitates, and adds hydrogen peroxide (H then
2O
2) be ferric iron to generate the superparamagnetism center with oxidation of divalent, separate with strong magnet again, obtain water dispersible magnetic high polymer microsphere at last.
In the step 1, be tert-butyl acrylate (tBA) or the vinyl monomer that contains tert-butyl ester base but described original position produces the polymer monomer at magnetic center.
In the step 1 and 2, described initiator is a persulfide, preferred Potassium Persulphate, Sodium Persulfate or ammonium persulphate; Described hydrophobic monomer is aromatic series alkene class or aliphatics unsaturated ester class, optimization styrene (St) or methacrylic ester (MMA); Described linking agent is Vinylstyrene (DVB), Ethylene glycol dimethacrylate (EGDMA), N, N '-methylene-bisacrylamide (NAPP) or diacetone-acryloamide(DAA) (DAAM).
In the step 1 and 2, the drop rate of described mix monomer is 0.5～2g/h; Stirring velocity is 200～500r/min.
In the step 2, described hydrophilic monomer is meant to have water-soluble or wetting ability by this monomer institute synthetic polymkeric substance, the small molecule monomer, propylene aldehydes monomer and the polyoxyethylene esters of acrylic acid macromonomer that contain hydrophilic functional groups (as hydroxyl or amino), preferred Hydroxyethyl acrylate (HEA) or poly glycol monomethyl ether acrylate (200) are (mPEG-methacrylate).
In the step 3, the temperature of described pre-freeze is-30～-60 ℃, and the time is 5～10 hours.
In the step 3, described vacuum drying temperature is-30～-60 ℃, and pressure is 0.4～0.8MPa, and the time is 12～24 hours.
In the step 3, the methyl alcohol dialysis is adopted in described dialysis, and the employing permission is 4000～20000 dialysis tubing through maximum molecular weight.
In the step 3, described ferrous ion (Fe
2+) compound is iron protochloride, ferrous sulfate or ferrous phosphate.
In the step 3, described alkali is sodium hydroxide or the ammoniacal liquor of 2Wt%.
In the step 3, the volume ratio of described trifluoroacetic acid and methylene dichloride is 1: 1～5, and hydrolysis time is 2～24 hours.
The present invention compared with prior art has following advantage and effect:
(1) the present invention adopts two step emulsifier-free emulsion polymerization in-situ methods to prepare magnetic macromolecular microsphere, and this method is implemented simple, and is economical and practical, both overcome the shortcoming of common emulsifier-free emulsion polymerization method and activation swelling method, combines both advantages again simultaneously.
(2) the present invention preparation the magnetic macromolecular microsphere monodispersity fine, the size distribution of microballoon has good water dispersible and biocompatibility than homogeneous.
(3) preparation method of the present invention can control the distribution of magnetic particle preferably, and the magnetic contrast between the microballoon is little, and magnetic content is bigger.
(4) microballoon of the present invention's preparation is pure, does not have non-specific cohesion impurity, at an easy rate it is scattered in again in the water and stable existence, stores and transports easily, can be applied to fields such as medical treatment, bio-science.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Embodiment 1
(1) prepares the seed polymer emulsion by the first step emulsifier-free emulsion polymerization, i.e. the preparation of stratum nucleare
Take by weighing 0.075g Potassium Persulphate (KPS) and place there-necked flask, add 100mL deionized water (DDIW) dissolving.Take by weighing the 0.75g tert-butyl acrylate again, 0.75g methyl methacrylate, 0.25g Ethylene glycol dimethacrylate places dropping funnel, start after mixing and stir and make the logical nitrogen of whole system 20 minutes, place oil bath to heat there-necked flask and the there-necked flask initiator solution is stabilized in about 60 ℃, slowly begins to drip mixed monomer solution then, drip off in the 3h, it is constant to continue holding temperature, reaction 8h.
(2) prepare polymer emulsion by the second step emulsifier-free emulsion polymerization with nucleocapsid structure
In the above-mentioned seed polymer emulsion that makes, add 0.02g Potassium Persulphate and 30ml deionized water, in dropping funnel, add 2.0g poly glycol monomethyl ether acrylate (Mn is 200), 3.0g vinylbenzene and 1.0g Ethylene glycol dimethacrylate also mix, start and stir and make the logical nitrogen of whole system 20 minutes, after there-necked flask placed oil bath to heat to treat that the there-necked flask fluid temperature went back up to 60 ℃ in 10～20 minutes, begin to drip the shell mix monomer, and strict control rate of addition, drip off whole monomers about about 4h, the reaction times is 8h.
(3) in-situ preparing high molecule magnetic microsphere
The polymer emulsion that step (2) is made prior to pre-freeze in-50 ℃ of refrigerators, then in freeze drier, is vacuum-drying 12 hours under the 0.640 MPa condition in-50 ℃, pressure after centrifugal treating, obtains the white powder product.
Take by weighing this white powder product 1.5g, methylene dichloride and trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 3: 1) disperse with 10ml, stirring is spent the night and is removed the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 13ml, again with the FeCl of dialyzate and 5Wt%
2Solution 15ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, the sodium hydroxide solution adjusting pH value that adds 2Wt% is 8, makes and carboxyl bonded ferrous iron precipitation, adds 5mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or γ-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 6 times, obtained water dispersible magnetic high polymer microsphere 1.2g.The diameter of gained magnetic macromolecular microsphere is 430nm, and magnetic content is 6.5%, and saturation magnetization is 2.7emu/g.
Embodiment 2
(1) prepares the seed polymer emulsion by the first step emulsifier-free emulsion polymerization, i.e. the preparation of stratum nucleare
Take by weighing 0.075g Potassium Persulphate (KPS) and place there-necked flask, add 100mL deionized water (DDIW) dissolving.Take by weighing the 1.5g tert-butyl acrylate again, 3.0g methyl methacrylate, 0.5g Ethylene glycol dimethacrylate places dropping funnel, start after mixing and stir and make the logical nitrogen of whole system 20 minutes, place oil bath to heat there-necked flask and the there-necked flask initiator solution is stabilized in about 70 ℃, slowly begins to drip mixed monomer solution then, drip off in the 3h, it is constant to continue holding temperature, reaction 8h.
(2) prepare polymer emulsion by the second step emulsifier-free emulsion polymerization with nucleocapsid structure
In the above-mentioned seed polymer emulsion that makes, add 0.02g Potassium Persulphate and 30ml deionized water, in dropping funnel, add 2.0g poly glycol monomethyl ether acrylate (Mn is 200), 7.0g vinylbenzene and 1.0g Ethylene glycol dimethacrylate also mix, start and stir and make the logical nitrogen of whole system 20 minutes, after there-necked flask placed oil bath to heat to treat that the there-necked flask fluid temperature went back up to 70 ℃ in 10～20 minutes, begin to drip the shell mix monomer, and strict control rate of addition, drip off whole monomers about about 6h.Reaction times is 8h.
(3) in-situ preparing high molecule magnetic microsphere
The polymer emulsion that step (2) is made prior to pre-freeze in-50 ℃ of refrigerators, then in freeze drier, is vacuum-drying 12 hours under the 0.640 MPa condition in-50 ℃, pressure after centrifugal treating, obtains the white powder product.
Take by weighing this white powder product 1.5g, methylene dichloride and trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 3: 1) disperse with 10ml, stirring is spent the night and is removed the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 13ml, again with the FeCl of dialyzate and 5Wt%
2Solution 15ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, the sodium hydroxide solution adjusting pH value that adds 2Wt% is 8, makes and carboxyl bonded ferrous iron precipitation, adds 5mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or γ-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 6 times, obtained water dispersible magnetic high polymer microsphere 1.1g.The diameter of gained magnetic macromolecular microsphere is 560nm, and magnetic content is 12.8%, and saturation magnetization is 5.9emu/g.
Embodiment 3
(1) prepares the seed polymer emulsion by the first step emulsifier-free emulsion polymerization, i.e. the preparation of stratum nucleare
Take by weighing 0.075g Potassium Persulphate (KPS) and place there-necked flask, add 100mL deionized water (DDIW) dissolving.Take by weighing the 3.0g tert-butyl acrylate again, 1.5g methyl methacrylate, 0.5g Ethylene glycol dimethacrylate places dropping funnel, start after mixing and stir and make the logical nitrogen of whole system 20 minutes, place oil bath to heat there-necked flask and the there-necked flask initiator solution is stabilized in about 70 ℃, slowly begins to drip mixed monomer solution then, drip off in the 3h, it is constant to continue holding temperature, reaction 8h.
(2) prepare polymer emulsion by the second step emulsifier-free emulsion polymerization with nucleocapsid structure
In the above-mentioned seed polymer emulsion that makes, add 0.02g Potassium Persulphate and 30ml deionized water, in dropping funnel, add 2.0g poly glycol monomethyl ether acrylate (Mn is 200), 7.0g vinylbenzene and 1.0g Ethylene glycol dimethacrylate also mix, start and stir and make the logical nitrogen of whole system 20 minutes, after there-necked flask placed oil bath to heat to treat that the there-necked flask fluid temperature went back up to 70 ℃ in 10～20 minutes, begin to drip the shell mix monomer, and strict control rate of addition, drip off whole monomers about about 6h.Reaction times is 8h.
(3) in-situ preparing high molecule magnetic microsphere
The polymer emulsion that step (2) is made prior to pre-freeze in-50 ℃ of refrigerators, then in freeze drier, is vacuum-drying 12 hours under the 0.640 MPa condition in-50 ℃, pressure after centrifugal treating, obtains the white powder product.
Take by weighing this white powder product 1.5g, methylene dichloride and trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 3: 1) disperse with 10ml, stirring is spent the night and is removed the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 13ml, again with the FeCl of dialyzate and 5Wt%
2Solution 15ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, the sodium hydroxide solution adjusting pH value that adds 2Wt% is 8, makes and carboxyl bonded ferrous iron precipitation, adds 5mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or γ-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 6 times, obtained water dispersible magnetic high polymer microsphere 1.0g.The diameter of gained magnetic macromolecular microsphere is 550nm, and magnetic content is 21.2%, and saturation magnetization is 8.6emu/g.
Embodiment 4
(1) prepares the seed polymer emulsion by the first step emulsifier-free emulsion polymerization, i.e. the preparation of stratum nucleare
Take by weighing 0.075g Potassium Persulphate (KPS) and place there-necked flask, add 100mL deionized water (DDIW) dissolving.Take by weighing the 6.0g tert-butyl acrylate again, 3.0g methyl methacrylate, 0.5g Ethylene glycol dimethacrylate places dropping funnel, start after mixing and stir and make the logical nitrogen of whole system 20 minutes, place oil bath to heat there-necked flask and the there-necked flask initiator solution is stabilized in about 70 ℃, slowly begins to drip mixed monomer solution then, drip off in the 5h, it is constant to continue holding temperature, reaction 10h.
(2) prepare polymer emulsion by the second step emulsifier-free emulsion polymerization with nucleocapsid structure
In the above-mentioned seed polymer emulsion that makes, add 0.02g Potassium Persulphate and 30ml deionized water, in dropping funnel, add 10.0g poly glycol monomethyl ether acrylate (Mn is 200), 12.0g vinylbenzene and 2.0g Ethylene glycol dimethacrylate also mix, start and stir and make the logical nitrogen of whole system 20 minutes, after there-necked flask placed oil bath to heat to treat that the there-necked flask fluid temperature went back up to 70 ℃ in 10～20 minutes, begin to drip the shell mix monomer, and strict control rate of addition, drip off whole monomers about about 9h.Reaction times is 12h.
(3) in-situ preparing high molecule magnetic microsphere
The polymer emulsion that step (2) is made prior to pre-freeze in-50 ℃ of refrigerators, then in freeze drier, is vacuum-drying 12 hours under the 0.640 MPa condition in-50 ℃, pressure after centrifugal treating, obtains the white powder product.
Take by weighing this white powder product 1.5g, methylene dichloride and trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 3: 1) disperse with 10ml, stirring is spent the night and is removed the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 13ml, again with the FeCl of dialyzate and 5Wt%
2Solution 15ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, the sodium hydroxide solution adjusting pH value that adds 2Wt% is 8, makes and carboxyl bonded ferrous iron precipitation, adds 5mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or γ-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 6 times, obtained water dispersible magnetic high polymer microsphere 0.9g.The diameter of gained magnetic macromolecular microsphere is 1200nm, and magnetic content is 33.6%, and saturation magnetization is 12.1emu/g.
Embodiment 5
(1) prepares the seed polymer emulsion by the first step emulsifier-free emulsion polymerization, i.e. the preparation of stratum nucleare
Take by weighing 0.075g Potassium Persulphate (KPS) and place there-necked flask, add 100mL deionized water (DDIW) dissolving.Take by weighing the 3.0g tert-butyl acrylate again, 1.5g vinylbenzene, 0.5g Ethylene glycol dimethacrylate places dropping funnel, start after mixing and stir and make the logical nitrogen of whole system 20 minutes, place oil bath to heat there-necked flask and the there-necked flask initiator solution is stabilized in about 70 ℃, slowly begins to drip mixed monomer solution then, drip off in the 3h, it is constant to continue holding temperature, reaction 8h.
(2) prepare polymer emulsion by the second step emulsifier-free emulsion polymerization with nucleocapsid structure
In the above-mentioned seed polymer emulsion that makes, add 0.02g Potassium Persulphate and 30ml deionized water, in dropping funnel, add the 2.0g Hydroxyethyl acrylate, 7.0g vinylbenzene and 1.0g Ethylene glycol dimethacrylate also mix, start and stir and make the logical nitrogen of whole system 20 minutes, after there-necked flask placed oil bath to heat to treat that the there-necked flask fluid temperature went back up to 70 ℃ in 10～20 minutes, begin to drip the shell mix monomer, and strict control rate of addition, drip off whole monomers about about 6h.Reaction times is 8h.
(3) in-situ preparing high molecule magnetic microsphere
The polymer emulsion that step (2) is made prior to pre-freeze in-50 ℃ of refrigerators, then in freeze drier, is vacuum-drying 12 hours under the 0.640 MPa condition in-50 ℃, pressure after centrifugal treating, obtains the white powder product.
Take by weighing this white powder product 1.5g, methylene dichloride and trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 3: 1) disperse with 10ml, stirring is spent the night and is removed the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 13ml, again with the FeCl of dialyzate and 5Wt%
2Solution 15ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, the sodium hydroxide solution adjusting pH value that adds 2Wt% is 8, makes and carboxyl bonded ferrous iron precipitation, adds 5mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or γ-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 6 times, obtained water dispersible magnetic high polymer microsphere 1.0g.The diameter of gained magnetic macromolecular microsphere is 610nm, and magnetic content is 19.6%, and saturation magnetization is 8.1emu/g.
Embodiment 6
(1) prepares the seed polymer emulsion by the first step emulsifier-free emulsion polymerization, i.e. the preparation of stratum nucleare
Take by weighing 0.075g Potassium Persulphate (KPS) and place there-necked flask, add 100mL deionized water (DDIW) dissolving.Take by weighing 3.0g methacrylic tert-butyl acrylate again, 1.5g t-butyl styrene, 0.5g Ethylene glycol dimethacrylate places dropping funnel, start after mixing and stir and make the logical nitrogen of whole system 20 minutes, place oil bath to heat there-necked flask and the there-necked flask initiator solution is stabilized in about 70 ℃, slowly begins to drip mixed monomer solution then, drip off in the 3h, it is constant to continue holding temperature, reaction 8h.
(2) prepare polymer emulsion by the second step emulsifier-free emulsion polymerization with nucleocapsid structure
In the above-mentioned seed polymer emulsion that makes, add 0.02g Potassium Persulphate and 30ml deionized water, in dropping funnel, add 2.0g poly glycol monomethyl ether acrylate (Mn is 200), 7.0g methyl methacrylate and 1.0g Ethylene glycol dimethacrylate also mix, start and stir and make the logical nitrogen of whole system 20 minutes, after there-necked flask placed oil bath to heat to treat that the there-necked flask fluid temperature went back up to 70 ℃ in 10～20 minutes, begin to drip the shell mix monomer, and strict control rate of addition, drip off whole monomers about about 6h.Reaction times is 8h.
(3) in-situ preparing high molecule magnetic microsphere
The polymer emulsion that step (2) is made prior to pre-freeze in-50 ℃ of refrigerators, then in freeze drier, is vacuum-drying 12 hours under the 0.640 MPa condition in-50 ℃, pressure after centrifugal treating, obtains the white powder product.
Take by weighing this white powder product 1.5g, methylene dichloride and trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 3: 1) disperse with 10ml, stirring is spent the night and is removed the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 13ml, again with the FeCl of dialyzate and 5Wt%
2Solution 15ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, the sodium hydroxide solution adjusting pH value that adds 2Wt% is 8, makes and carboxyl bonded ferrous iron precipitation, adds 5mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or γ-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 6 times, obtained water dispersible magnetic high polymer microsphere 1.0g.The diameter of gained magnetic macromolecular microsphere is 520nm, and magnetic content is 17.8%, and saturation magnetization is 7.6emu/g.
Embodiment 7
(1) prepares the seed polymer emulsion by the first step emulsifier-free emulsion polymerization, i.e. the preparation of stratum nucleare
Take by weighing 0.075g Potassium Persulphate (KPS) and place there-necked flask, add 100mL deionized water (DDIW) dissolving.Take by weighing the 3.0g tert-butyl acrylate again, 1.5g methyl methacrylate, 0.5g Ethylene glycol dimethacrylate places dropping funnel, start after mixing and stir and make the logical nitrogen of whole system 20 minutes, place oil bath to heat there-necked flask and the there-necked flask initiator solution is stabilized in about 70 ℃, slowly begins to drip mixed monomer solution then, drip off in the 3h, it is constant to continue holding temperature, reaction 8h.
(2) prepare polymer emulsion by the second step emulsifier-free emulsion polymerization with nucleocapsid structure
In the above-mentioned seed polymer emulsion that makes, add 0.02g Potassium Persulphate and 30ml deionized water, in dropping funnel, add 2.0g poly glycol monomethyl ether acrylate (Mn is 200), 7.0g methyl methacrylate and 1.0g Ethylene glycol dimethacrylate also mix, start and stir and make the logical nitrogen of whole system 20 minutes, after there-necked flask placed oil bath to heat to treat that the there-necked flask fluid temperature went back up to 70 ℃ in 10～20 minutes, begin to drip the shell mix monomer, and strict control rate of addition, drip off whole monomers about about 6h.Reaction times is 8h.
(3) in-situ preparing high molecule magnetic microsphere
The polymer emulsion that step (2) is made prior to pre-freeze in-50 ℃ of refrigerators, then in freeze drier, is vacuum-drying 12 hours under the 0.640 MPa condition in-50 ℃, pressure after centrifugal treating, obtains the white powder product.
Take by weighing this white powder product 1.5g, methylene dichloride and trifluoroacetic acid solution (methylene dichloride: trifluoroacetic acid volume ratio 3: 1) disperse with 10ml, stirring is spent the night and is removed the tertiary butyl in the cross-linking products with hydrolysis, product is with the methyl alcohol dialysis, then with the abundant dialysis of water, obtain emulsion 13ml, again with the FeCl of dialyzate and 5Wt%
2Solution 15ml mixes sealing, stirs 18 hours, and mixed solution is removed unnecessary FeCl with the water dialysis
2, the sodium hydroxide solution adjusting pH value that adds 2Wt% is 8, makes and carboxyl bonded ferrous iron precipitation, adds 5mL hydrogen peroxide (H then
2O
2) be ferric iron with oxidation of divalent, form Z 250 or γ-ferric oxide to generate the superparamagnetism center, stirring reaction separated with strong magnet after 8 hours, washed 6 times, obtained water dispersible magnetic high polymer microsphere 1.0g.The diameter of gained magnetic macromolecular microsphere is 580nm, and magnetic content is 23.5%, and saturation magnetization is 9.2emu/g.
Embodiment 8～11 related conditional parameters see Table 1, and other steps are with embodiment 1.
Table 1
| Embodiment | Mass ratio (KPS: M1: M2: EGD MA) in the step (1) between initiator and each monomer | Mass ratio (KPS: M3: M4: EGDMA) in the step (2) between initiator and each monomer | Temperature in the step (1), (2) (℃), the time (h) | Diameter of micro ball (nm) | Magnetic content (%) | Saturation magnetization (emu/g) |
| 1 | 1∶10∶10∶3.3 | 1∶100∶150∶50 | 60，8 | 430 | 6.5 | 2.7 |
| 2 | 1∶20∶40∶6.7 | 1∶100∶350∶50 | 70，8 | 560 | 12.8 | 5.9 |
| 3 | 1∶40∶20∶6.7 | 1∶100∶350∶50 | 70，8 | 550 | 21.2 | 8.6 |
| 4 | 1∶80∶40∶6.7 | 1∶500∶600∶100 | 70，8 | 1200 | 33.6 | 12.1 |
| 5 | 1∶40∶20∶6.7 | 1∶100∶350∶50 | 70，8 | 610 | 19.6 | 8.1 |
| 6 | 1∶40∶20∶6.7 | 1∶100∶350∶50 | 70，8 | 520 | 17.8 | 7.6 |
| 7 | 1∶40∶20∶6.7 | 1∶100∶350∶50 | 70，8 | 580 | 23.5 | 9.2 |
| 8 | 1∶40∶20∶6.7 | 1∶200∶250∶50 | 70，8 | 530 | 22.7 | 8.9 |
| 9 | 1∶40∶20∶6.7 | 1∶350∶150∶50 | 70，8 | 500 | 24.3 | 9.4 |
| 10 | 1∶60∶30∶6.7 | 1∶400∶500∶100 | 70，12 | 920 | 31.2 | 11.3 |
| 11 | 1∶53.4∶6.7∶6.7 | 1∶100∶350∶50 | 70，12 | 570 | 29.1 | 10.9 |
Annotate: embodiment 1,2, M1 in 3,4,8,9,10,11, and M2, M3, M4 is respectively tert-butyl acrylate, methyl methacrylate, poly glycol monomethyl ether acrylate (Mn is 200), vinylbenzene; Be respectively tert-butyl acrylate among the embodiment 5, vinylbenzene, Hydroxyethyl acrylate, vinylbenzene; Be respectively the methacrylic tert-butyl acrylate among the embodiment 6, t-butyl styrene, poly glycol monomethyl ether acrylate (Mn is 200), methyl methacrylate; Be respectively tert-butyl acrylate among the embodiment 7, methyl methacrylate, poly glycol monomethyl ether acrylate (Mn is 200), methyl methacrylate;
Claims (10)
1, a kind of water dispersible magnetic high polymer microsphere, it is characterized in that: by inorganic superparamagnetism center and the common mixture of forming of high molecular polymer, but internal layer is to have original position to produce the polymer monomer at magnetic center and the multipolymer of hydrophobic monomer, forms by the first step emulsifier-free emulsion polymerization; Skin is the multipolymer of hydrophilic monomer and hydrophobic monomer, is formed by the second step emulsifier-free emulsion polymerization; Between internal layer and the outer field polymkeric substance is random copolymerization.
2, water dispersible magnetic high polymer microsphere according to claim 1 is characterized in that: described hydrophilic monomer is small molecule monomer, propylene aldehydes monomer and the polyoxyethylene esters of acrylic acid macromonomer that contains hydrophilic functional groups.
3, water dispersible magnetic high polymer microsphere according to claim 1 is characterized in that: described hydrophobic monomer is aromatic series alkene class or aliphatics unsaturated ester class.
4, water dispersible magnetic high polymer microsphere according to claim 1 is characterized in that: but described original position produces the polymer monomer at magnetic center is tert-butyl acrylate or the vinyl monomer that contains tert-butyl ester base.
5, water dispersible magnetic high polymer microsphere according to claim 1 is characterized in that: described inorganic superparamagnetic material is for having paramagnetic inorganic metal or its oxide compound.
6, a kind of preparation method of each described water dispersible magnetic high polymer microsphere of claim 1～5 is characterized in that comprising the steps:
(1) but make by the first step emulsifier-free emulsion polymerization and to have the polymkeric substance " nuclear " that original position produces the magnetic center, i.e. the preparation of stratum nucleare: the initiator of adding 1 mass parts and the deionized water of 1000～1500 mass parts in reaction vessel earlier; The polymer monomer that simultaneously but the original position of the linking agent of the hydrophobic monomer of 3.3～50 mass parts, 3.3～10 mass parts and 10～100 mass parts is produced the magnetic center mixes and obtains mix monomer; In atmosphere of inert gases with under stirring, mix monomer is added in the above-mentioned reaction vessel that initiator and deionized water be housed, temperature of reaction is 50～90 ℃, the reaction times is 6～24 hours, obtains the seed polymer emulsion;
(2) by the final polymer microballoon that forms of the second step emulsifier-free emulsion polymerization: in above-mentioned seed polymer emulsion, add the initiator of 0.2～0.4 mass parts and the deionized water of 300～500 mass parts with nucleocapsid structure, temperature is raised to 50～90 ℃, add the shell mix monomer that the linking agent by the shell hydrophobic monomer of the shell hydrophilic monomer of 20～200 mass parts, 30～240 mass parts and 10～40 mass parts mixes then in atmosphere of inert gases with under stirring, reaction times is 6～24 hours, obtains polymer emulsion;
(3) in-situ preparing high molecule magnetic microsphere: polymer emulsion pre-freeze after centrifugal treating that step 2 is made, carry out vacuum-drying then, adopt the mixing solutions of trifluoroacetic acid and methylene dichloride to disperse hydrolysis again, the gained hydrolysate is removed small molecular weight impurity through dialysis earlier, again dialyzate is mixed with volume ratio 1: 0.5～2 with the ferrous ion compound solution and stir, and to regulate the pH value with alkali be 7～9, make with carboxyl bonded ferrous iron and precipitate, adding hydrogen peroxide then is that ferric iron is to generate the superparamagnetism center with oxidation of divalent, separate with strong magnet again, obtain water dispersible magnetic high polymer microsphere at last.
7, the preparation method of water dispersible magnetic high polymer microsphere according to claim 6 is characterized in that: in the step 1, be tert-butyl acrylate or the vinyl monomer that contains tert-butyl ester base but described original position produces the polymer monomer at magnetic center.
8, the preparation method of water dispersible magnetic high polymer microsphere according to claim 6 is characterized in that: in the step 1 and 2, described initiator is a persulfide; Described hydrophobic monomer is aromatic series alkene class or aliphatics unsaturated ester class; Described linking agent is Vinylstyrene, Ethylene glycol dimethacrylate, N, N '-methylene-bisacrylamide or diacetone-acryloamide(DAA).
9, the preparation method of water dispersible magnetic high polymer microsphere according to claim 6, it is characterized in that: in the step 2, described hydrophilic monomer is the macromonomer of the small molecule monomer, propylene aldehydes monomer and the polyoxyethylene esters of acrylic acid that contain hydrophilic functional groups.
10, the preparation method of water dispersible magnetic high polymer microsphere according to claim 6 is characterized in that: in the step 3, the volume ratio of described trifluoroacetic acid and methylene dichloride is 1:1～5, and hydrolysis time is 2～24 hours.
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| CN103509143A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of organic/inorganic composite globules |
| CN114736402A (en) * | 2022-03-29 | 2022-07-12 | 江苏月旭新材料科技有限公司 | Polymer nano magnetic bead and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103509143A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Preparation method of organic/inorganic composite globules |
| CN103509143B (en) * | 2012-06-27 | 2016-01-20 | 中国石油化工股份有限公司 | The preparation method of organic/inorganic composite pellets |
| CN114736402A (en) * | 2022-03-29 | 2022-07-12 | 江苏月旭新材料科技有限公司 | Polymer nano magnetic bead and preparation method and application thereof |
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