CN101559343B - Method for preparing magnetic temperature-sensitive composite microsphere with nuclear shell structure by adopting in-situ grafting technique - Google Patents
Method for preparing magnetic temperature-sensitive composite microsphere with nuclear shell structure by adopting in-situ grafting technique Download PDFInfo
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- CN101559343B CN101559343B CN2009100494231A CN200910049423A CN101559343B CN 101559343 B CN101559343 B CN 101559343B CN 2009100494231 A CN2009100494231 A CN 2009100494231A CN 200910049423 A CN200910049423 A CN 200910049423A CN 101559343 B CN101559343 B CN 101559343B
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Abstract
The invention belongs to the technical field of medical engineering of polymer material and dust, in particular to a method for preparing magnetic temperature-sensitive composite microsphere with nuclear shell structure by adopting in-situ grafting technique. The preparation method comprises the following steps: carrying out surface modification to ferroferric oxide nano magnetic particles, leading the surface thereof to be carried with polymerisable double bonds, utilizing reversible addition-fragmentation chain transfer (RAFT) polymerization technique, carrying out in-situ grafting polymerization to N-isopropylacrylamide and hydrophilic allyl monomer on the surface of the magnetic particles to form a temperature-sensitive polymer, and obtaining the nuclear shell structure composite material with temperature-sensitive hydrophilic shell and controllable magnetothermal effect magnetic nuclear. The nuclear shell structure composite material has magnetothermal effect of ferroferric oxide,magnetic positioning capability and temperature responsiveness of the temperature-sensitive polymer simultaneously, and has wide application in fields of control release, immunoassay, memory elementswitches and sensors and the like. The synthesis method is simple and easy to operate, and the materials can be produced industrially, thus having good promotion and application values.
Description
Technical field
The invention belongs to macromolecular material and biomedical engineering technology field, be specifically related to the method that a kind of situ-formed graft technology prepares magnetic temperature-sensitive composite microsphere with nuclear shell structure.
Background technology
Polymer-modified magnetic particle is owing to have the surface-functional of polymer concurrently and the magnetic responsiveness of magnetic nuclear, is widely used in biochemical fields such as immobilised enzymes, cell are preferred, Protein Separation, targeted drug.Comparatively the preparation method of Cheng Shu magnetic polymer particulate is a monomer polymerization method, comprises suspension polymerization, emulsion polymerization, dispersion copolymerization method etc.What but above-mentioned several preparation means adopted usually is conventional free radical polymerisation process, the shell polymer molecular weight is wayward, and mostly be remote force (Van der Waals force, hydrogen bond) combination between strand and stratum nucleare inorganic particulate, interaction force a little less than, particulate nuclear-shell the adhesion that makes is poor, particle diameter is big, and it is wide to distribute, and magnetic content is low.
In recent years, along with controlled " activity " radical polymerization technique is more and more in the correlative study in Polymer Synthesizing field, uses ATRP (ATRP) and as active free radical polymerization (NMRP) technology of media the magnetic particle surface is modified and see report (Eizo Marutanil in succession with NO free radical; Shinpei Yamamoto; TsedevNinjbadgar; Yoshinobu Tsujii; Takeshi Fukuda; Mikio Takano, Polymer 2004,45,2231-2235; Yabin Sun; Xiaobin Ding; Zhaohui Zheng; Xu Cheng; Xinhua Hu; Yuxing Peng, EuropeanPolymer Journal 2007,43,762-772).The basic thought of this type of work is to make the free radical activity kind be anchored to the magnetic particle surface by suitable way, trigger monomer polymerization then, in polymerization process, the strand that increases is in this dynamic competition of activity/inactivation all the time, so the degree of polymerization can not instantaneously increase suddenly, at the differential responses time point, adopt certain technology that the segment inactivation of growth, polymerization are stopped, thereby realize the effective regulation and control of magnetic particle surface polymer molecular weight and the accurate control of surface texture.
At present, caused interest (the James J.Lai of Many researchers about the research work of preparation magnetic temperature-sensitive composite microsphere that temperature sensitive polymer is combined with magnetic nano-particle; John M.Hoffman; Mitsuhiro Ebara; Allan S.Hoffman; Claude Estourne; Alain Wattiaux; Patrick S.Stayton, Langmuir 2007,23,7385-7391).Wherein temperature sensitive polymer chosen mostly have excellent temperature-responsive and biocompatibility poly-(N-N-isopropylacrylamide) (PNIPAAm) and copolymer, this type of research focuses mostly in targeted drug transmission aspect, the magnetic that purpose is to utilize magnetic nuclear is positioned the magnetic temperature-sensitive composite microsphere of medicine carrying for the lesion, utilizes the temperature-sensitive switch of shell polymer to discharge medicine again.
Summary of the invention
The object of the present invention is to provide a kind of situ-formed graft technology to prepare the method for magnetic temperature-sensitive composite microsphere with nuclear shell structure.The temperature sensitivity of polymer and the magnetic responsiveness of magnetic nuclear are combined, can be applicable to the targeted drug transmission.The present invention has adopted reversible addition-fracture chain transfer polymerization (RAFT) technology that rarely has report, the free radical activity kind is anchored to the magnetic particle surface, trigger monomer polymerization then prepares a series of magnetic temperature-sensitive composite microspheres with different lower critical solution temperatures (LCST).
The situ-formed graft technology that the present invention proposes prepares the method for magnetic temperature-sensitive composite microsphere with nuclear shell structure, and concrete steps are as follows:
(1) be in the silane coupler KH-570 ethanolic solution of 0.5%-50% in mass concentration, adding mass concentration is the ultrasonic dispersion of 0.1%-10% ferriferrous oxide nano magnetic particle, reaction temperature is 50～70 ℃, reaction time is 0.2～30 hour, product process magnetic separates the back and cleans (being generally 3-5 time) several times with solvent orange 2 A, puts into the vacuum drying oven drying;
(2) magnetic particle with step (1) gained drying is scattered among the solvent B;
(3) in the magnetic particle solution of step (2), add monomer N-N-isopropylacrylamide (NIPAAm), hydrophilic monomer C, initator D and RAFT chain-transferring agent E, carry out polymerisation in solution, polymerization temperature is 20～150 ℃, polymerization time is 1～240 hour, after the product that makes precipitation, vacuum drying, obtain magnetic temperature-sensitive composite microsphere; Monomer N-N-isopropylacrylamide (NIPAAm) is 10～1000: 0～1000 with the mol ratio of hydrophilic monomer C, the addition of initator D is monomer N-N-isopropylacrylamide (NIPAAm) and 0.01～5% of hydrophilic monomer C integral molar quantity, and the addition of RAFT chain-transferring agent E is 1-10 a times of initator D amount of substance.
Among the present invention, solvent orange 2 A is absolute ethyl alcohol, acetone, methyl alcohol, oxolane, dioxane, N described in the step (1), dinethylformamide, N, and N-DEF, N, one in N-dimethylacetylamide or the dimethyl sulfoxide (DMSO) is to several.
Among the present invention, solvent B is water, oxolane, dioxane, N described in the step (2), dinethylformamide, N, and N-DEF, N, one in N-dimethylacetylamide or the dimethyl sulfoxide (DMSO) is to several.
Among the present invention, hydrophilic monomer C is N,N-DMAA or N described in the step (3), in the N-diethyl acrylamide one to two kind.
Among the present invention, initator D described in the step (3) be in azodiisobutyronitrile, ABVN, benzoyl peroxide, diacetyl peroxide, peroxidating two (2, the 4-dichloro-benzoyl), dioctanoyl peroxide, dilauroyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, isopropyl benzene hydroperoxide, TBHP, peroxy dicarbonate diisobutyl ester, persulfate (potassium, sodium or ammonium salt) or the hydrogen peroxide any.
Among the present invention, RAFT chain-transferring agent E described in the step (3) is that the withered ester of dithiobenzoic acid, two sulfo-s β-naphthoic acid isobutyronitrile ester, isocyano group propyl disulfide are for benzoic ether, dithiobenzoic acid (4-cyanopentanoic acid) ester, dithiobenzoic acid isobutyronitrile, dithiobenzoic acid phenethyl ester, dithiobenzoic acid cumenyl ester, dithiobenzoic acid benzyl ester, the different phenylpropyl alcohol ester of phenyl methyl-carbithionic acid, α-two sulfo-naphthoic acid isobutyronitrile ester or S, arbitrary in S '-two (α, the α ' dimethyl-α acetate) trithiocarbonate to several.
Gained complex microsphere of the present invention is a nucleocapsid structure, and described nuclear is the ferriferrous oxide nano magnetic particle with the co-precipitation legal system, and shell is a temperature sensing polymer, and the particle diameter of this complex microsphere is single and disperses and in the 30nm-500nm scope.
The invention has the advantages that: raw material sources are extensive, but the equal suitability for industrialized production of used N-N-isopropylacrylamide, hydrophilic monomer and ferriferrous oxide nano-particle, and synthetic method is simple.Synthetic magnetic temperature-sensitive composite microsphere possesses temperature sensitivity and magnetic property simultaneously, synthesizing of shell copolymer owing to adopted the method for RAFT living polymerization, its thickness and molecular weight can be regulated by changing monomer consumption and initator chain-transferring agent ratio, and lower critical solution temperature (LCST) can be regulated by adding hydrophilic monomer B.Magnetic temperature-sensitive composite microsphere of the present invention has widely in fields such as control release, memory cell switch, sensors to be used.
Description of drawings
Fig. 1 is the structural representation of the magnetic temperature-sensitive composite microsphere of embodiment 1 preparation.MnZn is than being x: 1-x in the magnetic particle, and x is 0-1.
Fig. 2 is that the light transmittance of the magnetic temperature-sensitive composite microsphere aqueous solution of embodiment 1 preparation is with the variation of temperature situation.
The specific embodiment
Following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
In the silane coupler KH-570 of 100ml5% ethanolic solution, add the ultrasonic dispersion of 0.5g ferriferrous oxide nano magnetic particle, rising temperature to 60 ℃ reaction 6 hours, product separates the back through magnetic and cleans five times with ethanol, puts into the vacuum drying oven drying.The dry magnetic particle that makes is scattered in 50mlN, in the dinethylformamide, take by weighing 1.13g monomer N-N-isopropylacrylamide (NIPAAm), 1.00g N, N-DMAA, 0.33g azodiisobutyronitrile, 0.96g isocyano group propyl disulfide are for benzoic ether, carry out polymerisation in solution, polymerization temperature is 80 ℃, polymerization time is 3 hours, with the product magnetic that makes separate, after the vacuum drying, obtain magnetic temperature-sensitive composite microsphere, the particle diameter of this complex microsphere is single and disperses and in the 30nm-500nm scope.Fig. 1 is the molecular structural formula of magnetic composite microsphere, and this complex microsphere has responsive to temperature characteristic preferably as can be seen from Fig. 2.
Embodiment 2
In the silane coupler KH-570 of 500ml6% ethanolic solution, add the ultrasonic dispersion of 10g ferriferrous oxide nano magnetic particle, rising temperature to 50 ℃ reaction 16 hours, product separates the back through magnetic and cleans five times with acetone, puts into the vacuum drying oven drying.The dry magnetic particle that makes is scattered in 250ml 1, in the 4-dioxane, take by weighing 22.6g monomer N-N-isopropylacrylamide (NIPAAm), 40.0gN, N-diethyl acrylamide, 0.6568g benzoyl peroxide, 3.24g dithiobenzoic acid cumenyl ester, carry out polymerisation in solution, polymerization temperature is 75 ℃, and polymerization time is 6 hours, the product magnetic that makes is separated, after the vacuum drying, obtains magnetic temperature-sensitive composite microsphere.The particle diameter of this complex microsphere is single and disperses and in the 30nm-500nm scope.Figure .1 is the molecular structural formula of magnetic composite microsphere, and this complex microsphere has responsive to temperature characteristic preferably as can be seen from Fig. 2.
Embodiment 3
In the silane coupler KH-570 of 1000ml4% ethanolic solution, add the ultrasonic dispersion of 15g ferriferrous oxide nano magnetic particle, rising temperature to 70 ℃ reaction 10 hours, product separates the back through magnetic and cleans five times with oxolane, puts into the vacuum drying oven drying.The dry magnetic particle that makes is scattered in 150ml N, in the N-DEF, takes by weighing 11.3g monomer N-N-isopropylacrylamide (NIPAAm), 10.0gN, the N-DMAA, 10.0gN, N-diethyl acrylamide, 0.3284g dilauroyl peroxide, 1.21g α-two sulfo-naphthoic acid isobutyronitrile ester, carry out polymerisation in solution, polymerization temperature is 70 ℃, and polymerization time is 8 hours, the product magnetic that makes is separated, after the vacuum drying, obtains magnetic temperature-sensitive composite microsphere.The particle diameter of this complex microsphere is single and disperses and in the 30nm-500nm scope.Fig. 1 is the molecular structural formula of magnetic composite microsphere, and this complex microsphere has responsive to temperature characteristic preferably as can be seen from Fig. 2.
Embodiment 4
In the silane coupler KH-570 of 2000ml15% ethanolic solution, add the ultrasonic dispersion of 2.0g ferriferrous oxide nano magnetic particle, rising temperature to 75 ℃ reaction 9 hours, product separates back N through magnetic, dinethylformamide cleans five times, puts into the vacuum drying oven drying.The dry magnetic particle that makes is scattered in the 100ml dimethyl sulfoxide (DMSO), take by weighing 11.3g monomer N-N-isopropylacrylamide (NIPAAm), 20.0gN, the N-DMAA, 0.3284g isopropyl benzene hydroperoxide, the different phenylpropyl alcohol ester of 1.53g phenyl methyl-carbithionic acid carries out polymerisation in solution, polymerization temperature is 85 ℃, polymerization time is 3 hours, and the product magnetic that makes is separated, after the vacuum drying, obtains magnetic temperature-sensitive composite microsphere.The particle diameter of this complex microsphere is single and disperses and in the 30nm-500nm scope.Fig. 1 is the molecular structural formula of magnetic composite microsphere, and this complex microsphere has responsive to temperature characteristic preferably as can be seen from Fig. 2.
Claims (2)
1. a situ-formed graft technology prepares the method for magnetic temperature-sensitive composite microsphere with nuclear shell structure, it is characterized in that concrete steps are as follows:
(1) be in the silane coupler KH-570 ethanolic solution of 0.5%-50% in mass concentration, adding mass concentration is the ultrasonic dispersion of ferriferrous oxide nano magnetic particle of 0.1%-15%, reaction temperature is 50～70 ℃, reaction time is 0.2～30 hour, product separates the back through magnetic and cleans with solvent orange 2 A, puts into the vacuum drying oven drying;
(2) magnetic particle with step (1) gained drying is scattered among the solvent B;
(3) in the magnetic particle solution of step (2), add monomer N-N-isopropylacrylamide, hydrophilic monomer C, initator D and RAFT chain-transferring agent E, carry out polymerisation in solution, polymerization temperature is 20～150 ℃, polymerization time is 1～240 hour, after the product that makes precipitation, vacuum drying, obtain magnetic temperature-sensitive composite microsphere; The mol ratio of monomer N-N-isopropylacrylamide and hydrophilic monomer C is 10～1000: 0～1000, the addition of initator D is 0.01～5% of monomer N-N-isopropylacrylamide and a hydrophilic monomer C integral molar quantity, and the addition of RAFT chain-transferring agent E is 1-10 a times of initator D amount of substance; Wherein:
Solvent orange 2 A is absolute ethyl alcohol, acetone, methyl alcohol, oxolane, dioxane, N described in the step (1), dinethylformamide, N, and N-DEF, N, one in N-dimethylacetylamide or the dimethyl sulfoxide (DMSO) is to several;
Solvent B is water, oxolane, dioxane, N described in the step (2), dinethylformamide, N, and N-DEF, N, one in N-dimethylacetylamide or the dimethyl sulfoxide (DMSO) is to several;
In hydrophilic monomer C described in the step (3) is N,N-DMAA or N, in the N-diethyl acrylamide one to two kind;
Initator D described in the step (3) be in azodiisobutyronitrile, ABVN, benzoyl peroxide, diacetyl peroxide, peroxidating two (2, the 4-dichloro-benzoyl), dioctanoyl peroxide, dilauroyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, peroxidized t-butyl perbenzoate, the peroxidating pivalic acid tert-butyl ester, isopropyl benzene hydroperoxide, TBHP, peroxy dicarbonate diisobutyl ester, persulfate or the hydrogen peroxide any;
RAFT chain-transferring agent E described in the step (3) is that the withered ester of dithiobenzoic acid, two sulfo-s β-naphthoic acid isobutyronitrile ester, isocyano group propyl disulfide are for benzoic ether, dithiobenzoic acid (4-cyanopentanoic acid) ester, dithiobenzoic acid isobutyronitrile, dithiobenzoic acid phenethyl ester, dithiobenzoic acid cumenyl ester, dithiobenzoic acid benzyl ester, the different phenylpropyl alcohol ester of phenyl methyl-carbithionic acid, α-two sulfo-naphthoic acid isobutyronitrile ester or S, arbitrary in S '-two (α, the α ' dimethyl-α acetate) trithiocarbonate to several.
2. situ-formed graft technology according to claim 1 prepares the method for magnetic temperature-sensitive composite microsphere with nuclear shell structure, it is characterized in that the gained complex microsphere is a nucleocapsid structure, described nuclear is the ferriferrous oxide nano magnetic particle with the co-precipitation legal system, shell is a temperature sensing polymer, the particle diameter of this complex microsphere is single dispersion, and particle diameter is 30nm-500nm.
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