CN1288179C - Process for preparing magnetic polymethyl methacrylate microsphere by two-step method - Google Patents
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- CN1288179C CN1288179C CN 200510034665 CN200510034665A CN1288179C CN 1288179 C CN1288179 C CN 1288179C CN 200510034665 CN200510034665 CN 200510034665 CN 200510034665 A CN200510034665 A CN 200510034665A CN 1288179 C CN1288179 C CN 1288179C
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Abstract
The present invention relates to a method for preparing a magnetic polymethyl methacrylate microsphere with a two-step method, which comprises two steps: step one, a polymethyl methacrylate microsphere is prepared; step two, a magnetic polymethyl methacrylate microsphere is prepared. The present invention overcomes the defects that the particle diameter distribution is wide, the magnetism content distribution is uneven and polymerizing conditions are difficult to control existing in the magnetic microsphere prepared by the suspension polymerization of a one-step method in the prior art. In the first stage, a methyl methacrylate microsphere is synthesized, and the particle diameter and the purity of the microsphere are controlled; in the polymerization of the second stage, Fe3O4 iron powder is embedded in the polymethyl methacrylate microsphere to obtain the magnetic polymethyl methacrylate microsphere. Thereby, the magnetic polymethyl methacrylate microsphere which has the advantages of suitable preparing particle diameter, high monodispersity, high magnetic responsivity, high mechanical stability, high acid resistance and good combination properties is obtained.
Description
Technical field
The present invention relates to be widely used in the method for the process for preparing magnetic polymethyl methacrylate microsphere by two-step of magneticsubstance, biomedicine (clinical diagnosis, targeted drug, enzyme mark), cytology (cell marking, cellular segregation etc.) and biotechnology (immobilization of enzyme), separation engineering and stealthy technique etc.
Background technology
Magnetic macromolecular microsphere is the microballoon with certain magnetic and special construction that organic polymer and inorganic magnetic material combine.Because of magnetic macromolecular microsphere has the numerous characteristics and the magnetic responsiveness of polymer microsphere simultaneously concurrently, not only can by methods such as copolymerization and surface modification give its surface functional group (as-OH ,-COOH ,-CHO ,-NH
2,-SH etc.), can also convenient separation promptly and directed under externally-applied magnetic field.
Magnetic macromolecular microsphere can be divided three classes by structure: the one, and nuclear is magneticsubstance, and shell is the nuclear/shell-type structure of polymkeric substance, forms nuclear by metal oxide (as oxide compounds such as iron, cobalt, nickel), and macromolecular material is formed shell; The 2nd, be nuclear with the macromolecular material, magneticsubstance is as the nuclear/shell-type structure of shell; The 3rd, internal layer, skin are all macromolecular material, and the middle layer is the sandwich type structural of magneticsubstance.The magnetic substance that the preparation magnetic microsphere is used usually has: straight iron powder, iron carbonyl, magnetite, positive wustite, ferrocobalt etc., and especially with Fe
3O
4Magnetic fluid is in the majority.The natural polymer that is used to prepare magnetic macromolecular microsphere mainly contains chitosan, gelatin, Mierocrystalline cellulose etc., and synthetic macromolecule mainly contains the comonomer of vinylbenzene or vinylbenzene and methyl methacrylate etc.
The widespread use of magnetic macromolecular microsphere requires it except that having uniform size distribution, suitable size and shape, also must possess as biocompatibility, stability and performance such as biodegradable.Also should consider dispersiveness, magnetic responsiveness and and the hydrophilic/hydrophobic on magnetic ball surface of magnetic microsphere simultaneously.
Main preparation method is entrapping method, letex polymerization, dispersion polymerization, suspension polymerization etc. at present.The method of magnetic microsphere is simple though entrapping method prepares, and the particle diameter of gained distributes wide, out-of-shape, and particle diameter is wayward, and impurity is more, and it is of limited application.Though letex polymerization and dispersion polymerization can obtain microballoon, owing to remove difficulty at the tensio-active agent (dispersion stabilizer) of microsphere surface absorption etc., the application on biotechnology is very restricted.The suspension polymerization process process is simple, and heat of polymerization is easy to get rid of, convenient operation and control, and polymkeric substance is easy to separation, washing, drying, and product is also comparatively pure, and can be directly used in forming process.Therefore the suspension polymerization development is very fast.How current magnetic macromolecular microsphere goes on foot suspension polymerization with one, its surface is not only adsorbed and is enclosed with the small molecules tensio-active agent, and it is dispersed very poor, methyl methacrylate polymerization condition and size etc. are difficult to control, the behavior that causes magnetic microsphere to show in solution and in the magnetic field has nothing in common with each other, thereby has limited its application.
Summary of the invention
The objective of the invention is to very wide and the inhomogeneous and unmanageable shortcoming of polymerizing condition of magnetic content distribution for the size distribution that overcomes the prepared magnetic microsphere of prior art single stage method suspension polymerization, a kind of method of process for preparing magnetic polymethyl methacrylate microsphere by two-step is provided, at fs synthesizing methylmethacrylate microballoon at first, the particle diameter and the purity of control microballoon; Then in the subordinate phase polymerization Fe
3O
4Iron powder is embedded in the poly (methyl methacrylate) micro-sphere, obtain magnetic polymethyl methacrylate microsphere, obtain a kind of magnetic polymethyl methacrylate microsphere for preparing that particle diameter is suitable, monodispersity good, magnetic responsiveness is high, has favorable mechanical stability and acid proof high comprehensive performance.
The method of process for preparing magnetic polymethyl methacrylate microsphere by two-step of the present invention comprises:
A kind of method of process for preparing magnetic polymethyl methacrylate microsphere by two-step is characterized in that comprising the steps:
The first step, the preparation poly (methyl methacrylate) micro-sphere comprises
(1) dispersion agent is dissolved in the distilled water;
(2) in methyl methacrylate, add initiator, and initiator is dissolved fully;
(3) the solution stirring heating that step (1) is obtained, and logical nitrogen is got rid of the oxygen in the container, when temperature reaches 60 ℃～95 ℃, adding consumption is the vitriol oil of 0.1%～0.3% quality of described solution, add the solution that step (2) obtains again, the solution equivalent that its consumption and step (1) obtain;
(4) reaction is after 2～4 hours down at 60～90 ℃, and the continuation reaction 2～4 hours that heats up again makes the slaking of poly (methyl methacrylate) micro-sphere complete reaction;
(5) wash dispersion agent in the reactant off with hydrochloric acid soln, wash product then to neutral, suction filtration, drying obtains poly (methyl methacrylate) micro-sphere;
In second step, the preparation magnetic polymethyl methacrylate microsphere comprises
(1) poly (methyl methacrylate) micro-sphere that the first step is obtained is dissolved in the solvent, adds Fe
3O
4, and stir its swelling is dispersed in wherein;
(2) dispersion agent is soluble in water, fully stirring makes it to dissolve fully;
(3) solution that step (1) obtained adds the solution that step (2) obtains, and stirs 18～36 hours, treat that wherein solvent evaporates is intact after, pour out product, wash drying.
The present invention more specifically comprises the steps:
The first step, the preparation poly (methyl methacrylate) micro-sphere comprises
(1) dispersion agent is dissolved in the distilled water; Described dispersion agent is wherein one or more mixtures of magnesium hydroxide, calcium phosphate, barium sulfate, and the mass ratio of dispersion agent and water is 1: 100～3: 100;
(2) in methyl methacrylate, add initiator, and initiator is dissolved fully; Described initiator is dibenzoyl peroxide or Diisopropyl azodicarboxylate, with the mass ratio of methyl methacrylate be 1: 100～3: 100;
(3) the solution stirring heating that step (1) is obtained, and logical nitrogen 30～90min gets rid of the oxygen in the container, when temperature reaches 60 ℃～95 ℃, adding consumption is the vitriol oil of 0.1%～0.3% quality of described solution, add the solution that step (2) obtains again, the solution equivalent that its consumption and step (1) obtain;
(4) reaction is after 2～4 hours down at 60～90 ℃, and the continuation reaction 2～4 hours that heats up again makes the slaking of poly (methyl methacrylate) micro-sphere complete reaction;
(5) wash dispersion agent in the reactant off with the hydrochloric acid soln of 3%～7% volume, wash product then to neutral, suction filtration, drying obtains poly (methyl methacrylate) micro-sphere.
In second step, the preparation magnetic polymethyl methacrylate microsphere comprises
(1) poly (methyl methacrylate) micro-sphere that the first step is obtained is dissolved in the solvent, stirs to add Fe after 18～24 hours
3O
4, and stir its swelling is dispersed in wherein; Described solvent is trichloromethane or acetone, with the mass ratio of poly (methyl methacrylate) micro-sphere be 10: 100～35: 100; Control methyl methacrylate and Fe
3O
4Mass ratio be 70～80: 20～30;
(2) dispersion agent is soluble in water, fully stirring makes it to dissolve fully, and dispersion agent is wherein one or more mixtures of polyvinyl alcohol, sodium lauryl sulphate, tween-80, and the mass ratio of dispersion agent and water is 2: 100～4: 100;
(3) solution that step (1) obtained adds the solution that step (2) obtains, and stirs 18～36 hours, treat that wherein solvent evaporates is intact after, pour out product, wash suction filtration, 45 ℃ of dryings are 24 hours in vacuum drying oven.
The present invention compared with prior art has following advantage and effect:
Adopt the magnetic polymethyl methacrylate microsphere size of the inventive method preparation even, and distribution of sizes is narrower, and good stability is arranged in water and acidic medium, the magnetic responsiveness height of magnetic ball, its magnetic content can reach 30%.Inorganic have very strong interaction with polymkeric substance, and its interface has the ideal adhesiveproperties, can eliminate two kinds of unmatched problems of material thermal expansivity of inorganics and polymkeric substance.The pattern subglobular of magnetic polymethyl methacrylate microsphere provided by the present invention, suitable, the narrow diameter distribution of its size, the stability in medium, magnetic responsiveness surpass the existing prepared magnetic polymethyl methacrylate microsphere of polymerization technique.This performance increase substantially particle diameter, size distribution and the purity of having controlled microballoon in can polymerization owing to poly (methyl methacrylate) micro-sphere in the fs, make in the polyreaction of subordinate phase, polymethylmethacrylate is at Fe
3O
4The particulate surface coats evenly, has improved polymethylmethacrylate and Fe
3O
4Particulate consistency and interaction.Adopt vibrating sample magnetometer (VSM) and scanning electronic microscope (SEM) to detect magnetism of magnetic microsphere energy and pattern, compare with traditional polymerization process, adopt the size of the magnetic polymethyl methacrylate microsphere of two steps suspension polymerization preparation to be about 95 μ m, the size distribution coefficient is 1.024, specific saturation magnetization is 17.5, and magnetzation curve demonstrates no hysteresis, equals at 0 o'clock at externally-applied magnetic field, residual magnetization and coercive force are 0, show that magnetic microsphere has superparamagnetism.
Description of drawings
Fig. 1 is the sem photograph of the magnetic polymethyl methacrylate microsphere for preparing of the present invention.
Embodiment
Embodiment 1
The method of process for preparing magnetic polymethyl methacrylate microsphere by two-step of the present invention comprises the steps:
The first step, preparation poly (methyl methacrylate) micro-sphere comprise
(1) dispersion agent is dissolved in the distilled water; Described dispersion agent is a magnesium hydroxide, with the mass ratio of water be 1: 100;
(2) in methyl methacrylate, add initiator, and initiator is dissolved fully; Described initiator is a dibenzoyl peroxide, with the mass ratio of methyl methacrylate be 2: 100;
(3) the solution stirring heating that step (1) is obtained, and the oxygen in the logical nitrogen 30min eliminating container, when temperature reached 75 ℃, adding consumption was the vitriol oil of 0.1% quality of described solution, add the solution that step (2) obtains again, the solution equivalent that its consumption and step (1) obtain;
(4) reaction is after 2 hours down at 60 ℃, and the continuation reaction 4 hours that heats up again makes the slaking of poly (methyl methacrylate) micro-sphere complete reaction;
(5) wash dispersion agent in the reactant off with the hydrochloric acid soln of 3% volume, wash product then to neutral, suction filtration, drying obtains poly (methyl methacrylate) micro-sphere.
In second step, the preparation magnetic polymethyl methacrylate microsphere comprises
(1) poly (methyl methacrylate) micro-sphere that the first step is obtained is dissolved in the solvent, stirs to add Fe after 18 hours
3O
4, and stir its swelling is dispersed in wherein; Described solvent is an acetone, with the mass ratio of poly (methyl methacrylate) micro-sphere be 10: 100; Control methyl methacrylate and Fe
3O
4Weight ratio be 75: 25;
(2) dispersion agent is soluble in water, fully stirring makes it to dissolve fully, and dispersion agent is a polyvinyl alcohol, and the mass ratio of dispersion agent and water is 4: 100;
(3) solution that step (1) obtained adds the solution that step (2) obtains, and stirs 36 hours, treat that wherein solvent evaporates is intact after, pour out product, wash suction filtration, 45 ℃ of dryings are 24 hours in vacuum drying oven.
Above-mentioned quality, weight unit are gram.
As shown in Figure 1, the mean diameter of microballoon is about 95 μ m, and the monodispersity of microballoon is good, and size evenly.This explanation the present invention adopts two step suspension polymerization methods can prepare big or small homogeneous, and the good magnetic microsphere of monodispersity.
Embodiment 2
The method of process for preparing magnetic polymethyl methacrylate microsphere by two-step of the present invention comprises the steps:
The first step, the preparation poly (methyl methacrylate) micro-sphere comprises
(1) dispersion agent is dissolved in the distilled water; Described dispersion agent is a calcium phosphate, with the mass ratio of water be 3: 100;
(2) in methyl methacrylate, add initiator, and initiator is dissolved fully; Described initiator is a Diisopropyl azodicarboxylate, with the mass ratio of methyl methacrylate be 1: 100;
(3) the solution stirring heating that step (1) is obtained, and the oxygen in the logical nitrogen 90min eliminating container, when temperature reached 60 ℃, adding consumption was the vitriol oil of 0.3% quality of described solution, add the solution that step (2) obtains again, the solution equivalent that its consumption and step (1) obtain;
(4) reaction is after 2.5 hours down at 90 ℃, and the continuation reaction 2 hours that heats up again makes the slaking of poly (methyl methacrylate) micro-sphere complete reaction;
(5) wash dispersion agent in the reactant off with the hydrochloric acid soln of 7% volume, wash product then to neutral, suction filtration, drying obtains poly (methyl methacrylate) micro-sphere.
In second step, the preparation magnetic polymethyl methacrylate microsphere comprises
(1) poly (methyl methacrylate) micro-sphere that the first step is obtained is dissolved in the solvent, stirs to add Fe after 24 hours
3O
4, and stir its swelling is dispersed in wherein; Described solvent is an acetone, with the mass ratio of poly (methyl methacrylate) micro-sphere be 35: 100; Control methyl methacrylate and Fe
3O
4Mass ratio be 80: 20;
(2) dispersion agent is soluble in water, fully stirring makes it to dissolve fully, and dispersion agent is polyvinyl alcohol and sodium lauryl sulphate, and mass ratio is 70: 30, and the mass ratio of dispersion agent and water is 3: 100;
(3) solution that step (1) obtained adds the solution that step (2) obtains, and stirs 18 hours, treat that wherein solvent evaporates is intact after, pour out product, wash suction filtration, 45 ℃ of dryings are 24 hours in vacuum drying oven.
The monodispersity of the microballoon that obtains is good, and size evenly, and mean diameter is 93 μ m.
Above-mentioned quality, weight unit are gram.
Embodiment 3
The method of process for preparing magnetic polymethyl methacrylate microsphere by two-step of the present invention comprises the steps:
The first step: the preparation poly (methyl methacrylate) micro-sphere comprises
(1) dispersion agent is dissolved in the distilled water; Described dispersion agent is calcium phosphate and barium sulfate, and its mass ratio is 80: 20, and the mass ratio of dispersion agent and water is 2: 100;
(2) in methyl methacrylate, add initiator, and initiator is dissolved fully; Described initiator is a dibenzoyl peroxide, with the mass ratio of methyl methacrylate be 3: 100;
(3) the solution stirring heating that step (1) is obtained, and the oxygen in the logical nitrogen 65min eliminating container, when temperature reached 95 ℃, adding consumption was the vitriol oil of 0.15% quality of described solution, add the solution that step (2) obtains again, the solution equivalent that its consumption and step (1) obtain;
(4) reaction is after 4 hours down at 75 ℃, and the continuation reaction 3.5 hours that heats up again makes the slaking of poly (methyl methacrylate) micro-sphere complete reaction;
(5) wash dispersion agent in the reactant off with the hydrochloric acid soln of 4.5% volume, wash product then to neutral, suction filtration, drying obtains poly (methyl methacrylate) micro-sphere.
In second step, the preparation magnetic polymethyl methacrylate microsphere comprises
(1) poly (methyl methacrylate) micro-sphere that the first step is obtained is dissolved in the solvent, stirs to add Fe after 20 hours
3O
4, and stir its swelling is dispersed in wherein; Described solvent is an acetone, with the mass ratio of poly (methyl methacrylate) micro-sphere be 20: 100; Control methyl methacrylate and Fe
3O
4Mass ratio be 70: 30;
(2) dispersion agent is soluble in water, fully stirring makes it to dissolve fully, and dispersion agent is sodium lauryl sulphate and tween-80, and its mass ratio is 80: 20, and the mass ratio of dispersion agent and water is 2: 100;
(3) solution that step (1) obtained adds the solution that step (2) obtains, and stirs 25 hours, treat that wherein solvent evaporates is intact after, pour out product, wash suction filtration, 45 ℃ of dryings are 24 hours in vacuum drying oven.
The monodispersity of the microballoon that obtains is good, and size evenly, and mean diameter is 97 μ m.
Above-mentioned quality, weight unit are gram.
Claims (2)
1, a kind of method of process for preparing magnetic polymethyl methacrylate microsphere by two-step is characterized in that comprising the steps:
The first step, the preparation poly (methyl methacrylate) micro-sphere comprises
(1) dispersion agent is dissolved in the distilled water; Described dispersion agent is wherein one or more mixtures of magnesium hydroxide, calcium phosphate, barium sulfate;
(2) in methyl methacrylate, add initiator, and initiator is dissolved fully;
(3) the solution stirring heating that step (1) is obtained, and logical nitrogen is got rid of the oxygen in the container, when temperature reaches 60 ℃～95 ℃, adding consumption is the vitriol oil of 0.1%～0.3% quality of described solution, add the solution that step (2) obtains again, the solution equivalent that its consumption and step (1) obtain;
(4) reaction is after 2～4 hours down at 60～90 ℃, and the continuation reaction 2～4 hours that heats up again makes the slaking of poly (methyl methacrylate) micro-sphere complete reaction;
(5) wash dispersion agent in the reactant off with hydrochloric acid soln, wash product then to neutral, suction filtration, drying obtains poly (methyl methacrylate) micro-sphere;
In second step, the preparation magnetic polymethyl methacrylate microsphere comprises
(1) poly (methyl methacrylate) micro-sphere that the first step is obtained is dissolved in the solvent, adds Fe
3O
4, and stir its swelling is dispersed in wherein;
(2) dispersion agent is soluble in water, fully stirring makes it to dissolve fully; Described dispersion agent is wherein one or more mixtures of polyvinyl alcohol, sodium lauryl sulphate, tween-80;
(3) solution that step (1) obtained adds the solution that step (2) obtains, and stirs 18～36 hours, treat that wherein solvent evaporates is intact after, pour out product, wash drying.
2, method according to claim 1 is characterized in that
The first step, the preparation poly (methyl methacrylate) micro-sphere comprises
(1) dispersion agent is dissolved in the distilled water; Described dispersion agent is wherein one or more mixtures of magnesium hydroxide, calcium phosphate, barium sulfate, and the mass ratio of dispersion agent and water is 1: 100～3: 100;
(2) in methyl methacrylate, add initiator, and initiator is dissolved fully; Described initiator is dibenzoyl peroxide or Diisopropyl azodicarboxylate, with the mass ratio of methyl methacrylate be 1: 100～3: 100;
(3) the solution stirring heating that step (1) is obtained, and logical nitrogen 30～90min gets rid of the oxygen in the container, when temperature reaches 60 ℃～95 ℃, adding consumption is the vitriol oil of 0.1%～0.3% quality of described solution, add the solution that step (2) obtains again, the solution equivalent that its consumption and step (1) obtain;
(4) reaction is after 2～4 hours down at 60～90 ℃, and the continuation reaction 2～4 hours that heats up again makes the slaking of poly (methyl methacrylate) micro-sphere complete reaction;
(5) wash dispersion agent in the reactant off with the hydrochloric acid soln of 3%～7% volume, wash product then to neutral, suction filtration, drying obtains poly (methyl methacrylate) micro-sphere;
In second step, the preparation magnetic polymethyl methacrylate microsphere comprises
(1) poly (methyl methacrylate) micro-sphere that the first step is obtained is dissolved in the solvent, stirs to add Fe after 18～24 hours
3O
4, and stir its swelling is dispersed in wherein; Described solvent is trichloromethane or acetone, with the mass ratio of poly (methyl methacrylate) micro-sphere be 10: 100～35: 100; Control methyl methacrylate and Fe
3O
4Mass ratio be 70～80: 20～30;
(2) dispersion agent is soluble in water, fully stirring makes it to dissolve fully, and dispersion agent is wherein one or more mixtures of polyvinyl alcohol, sodium lauryl sulphate, tween-80, and the mass ratio of dispersion agent and water is 2: 100～4: 100;
(3) solution that step (1) obtained adds the solution that step (2) obtains, and stirs 18～36 hours, treat that wherein solvent evaporates is intact after, pour out product, wash suction filtration, 45 ℃ of dryings are 24 hours in vacuum drying oven.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549270B (en) * | 2009-04-03 | 2012-03-28 | 西北工业大学 | Preparation method of magnetic polymer inorganic composite micro-sphere |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101054427B (en) * | 2007-06-21 | 2011-10-05 | 北京鼎国昌盛生物技术有限责任公司 | Method of synthesizing monodisperse micron-level poly(methyl methacrylate) micro-sphere |
| CN102070864B (en) * | 2010-12-18 | 2012-07-04 | 四川大学 | Nanoscale polymethylmethacrylate magnetic composite microsphere and preparation method thereof |
| CN104475164B (en) * | 2014-11-19 | 2016-06-29 | 辽宁大学 | A kind of preparation method of the modified sulfonic acid type poly (methyl methacrylate) micro-sphere of rhenium |
| CN104830827B (en) * | 2015-06-01 | 2016-05-11 | 北京中科紫鑫科技有限责任公司 | A kind of preparation method of magnetic immobilized luciferase |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101549270B (en) * | 2009-04-03 | 2012-03-28 | 西北工业大学 | Preparation method of magnetic polymer inorganic composite micro-sphere |
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