CN104448088A - Preparation method of temperature-sensitive anisotropic magnetic microcapsule - Google Patents
Preparation method of temperature-sensitive anisotropic magnetic microcapsule Download PDFInfo
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- CN104448088A CN104448088A CN201410612027.6A CN201410612027A CN104448088A CN 104448088 A CN104448088 A CN 104448088A CN 201410612027 A CN201410612027 A CN 201410612027A CN 104448088 A CN104448088 A CN 104448088A
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Abstract
The invention relates to a preparation method of a temperature-sensitive anisotropic magnetic microcapsule. According to the preparation method, a novel temperature-sensitive magnetic microcapsule with a core in an unsymmetrical structure inside a microsphere is designed. The microcapsule has high medicine loading capacity and can be stimulated by temperature to release medicines in a control way, and through selective modification, the core of the microcapsule can be unilaterally targeted to the diseased part so that unilateral or touch-point type medicine release can be realized. The wall of the magnetic microcapsule is formed by vinyl caprolactam, a crosslinking agent and an auxiliary monomer copolymer, the core of the microcapsule is not in the center of the microsphere, but is near the outer wall of one side of the microsphere and is hereby in an unsymmetrical structure, magnetic nano particles are uniformly distributed in the wall of the microcapsule, and the microsphere is sensitive to temperature. The temperature-responsive magnetic microcapsule in a special structure can be used for the fields of highly pertinent targeted administration, tracing and controlled release.
Description
Technical field
The present invention relates to a kind of preparation method of temperature sensitive type anisotropic magnetic microcapsule, be specifically related to exist the polymer phase of consistency difference, the preparation of temperature sensitive type anisotropic magnetic microcapsule that capsule-core phase, magnetic-particle are host component, employing be a step miniemulsion polymerization technique.
Background technology
Magnetic coupling microcapsule are widely used in the field such as medicine controlled releasing and transmission, microreactor, sensor and development as a representative class with its container effect, easily separated characteristic and biocompatibility and modifiability.Therefore, in its structure design and preparation method, scholars has carried out extensive work.Can be divided three classes by structure magnetic composite micro-capsule: (1) magnetic particle is present in cyst wall; (2) magnetic particle is present in the capsule-core of capsule with the form of core, shows as structure of ringing a bell; (3) take magnetic particle as the inorganic magnetic microcapsule of cyst wall.Magnetic microcapsules being carried out drug encapsulation and be used for the progress that drug controlled release is target administration field, is also one of main point of application of current magnetic microcapsules.Compared with other drug controlled release carrier, the capsule-core of magnetic microcapsules provides targeting as medicine storage warehouse, magnetic particle, shows and more significantly uses advantage.Many materials are selected is the main material of cyst wall of capsule, comprises mesoporous silicon oxide (CN201010524731.8), liposome (CN201010191017.1), silicon-dioxide/polystyrene complex (CN201210494970.2), macromolecular material (CN201210068292.3; CN201210081020.7), environment-responsive polymkeric substance (CN201110025545.4) etc.Contriver reports that in CN201010202184.1 a kind of vinylbenzene is the preparation method of the composite magnetic microcapsules of organic wall material main body, and capsule shows the asymmetry of capsule-core.But have not yet to see the relevant report of temperature sensitive type anisotropic magnetic microcapsule
Magnetic microcapsules target administration aspect, although target has improve utilization ratio of drug fully, reduced infringement to surrounding body, release that is one-sided or contact point type has remained the target that investigators pursue.
Summary of the invention
The technical problem solved
In order to avoid the deficiencies in the prior art part, the present invention proposes a kind of preparation method of temperature sensitive type anisotropic magnetic microcapsule, devise a kind of capsule-core presents the novel structure of unsymmetrical structure temperature sensitive type magnetic microcapsules in microballoon inside, this microcapsule drug loading is high, the Co ntrolled release of medicine can be carried out under the stimulation of temperature, and capsule-core side is targeted to diseased region after selective modification and is expected to realize one-sided or contact point type administration.
Technical scheme
A preparation method for temperature sensitive type anisotropic magnetic microcapsule, is characterized in that step is as follows:
Step 1: preparation massfraction is the water phase surfactant mixture of 0.05% ~ 0.5%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase;
Step 2: be dispersed in by magnetic nano-particle in the monomer mixed solution being dissolved with initiator, assistant for emulsifying agent and capsule-core phase, as oil phase, carries out the ultrasonic magnetic nano-particle that makes to oil phase dispersed; The mass ratio of described initiator, magnetic nano-particle, assistant for emulsifying agent, capsule-core phase and monomer mixed solution is 1:1 ~ 5:3 ~ 8:5 ~ 15:30 ~ 100; Described monomer mixed solution is made up of caprolactam, linking agent, auxiliary monomer, and the mass ratio of three is 1:0.8 ~ 2.4:2 ~ 5; Described auxiliary monomer is: vinylbenzene, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or glycidyl methacrylate;
Step 3: oil phase is joined in the container containing aqueous phase, the mass ratio of oil phase and aqueous phase is 1:10 ~ 25, opens and stirs pre-emulsification 10-30min;
Step 4: the system after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 15-30min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in;
Step 5: under mechanical stirring system temperature is risen to 70-90 DEG C, isothermal reaction 6-12h, is cooled to room temperature and obtains brown color emulsion;
Step 6: by obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Described tensio-active agent is: sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide or sodium lauryl sulphate.
Described magnetic nano-particle is: the nano ferriferrous oxide of surperficial oleic acid modified or ferric oxide.
Described initiator is: benzoyl peroxide or Diisopropyl azodicarboxylate.
Described assistant for emulsifying agent is: paraffin, Long carbon chain alkane or Long carbon chain aliphatics alcohols.
Described capsule-core is mutually: normal hexane, hexanaphthene, normal heptane, octane or Skellysolve A.
Beneficial effect
The preparation method of a kind of temperature sensitive type anisotropic magnetic microcapsule that the present invention proposes, devise a kind of capsule-core presents the novel structure of unsymmetrical structure temperature sensitive type magnetic microcapsules in microballoon inside, this microcapsule drug loading is high, the Co ntrolled release of medicine can be carried out under the stimulation of temperature, and capsule-core side is targeted to diseased region after selective modification and is expected to realize one-sided or contact point type administration.
Magnetic microcapsules cyst wall prepared by the present invention is made up of caprolactam, linking agent, auxiliary monomer multipolymer, capsule-core does not occupy microballoon center, but press close to side microballoon outer wall and present unsymmetrical structure, magnetic nano-particle is dispersed in cyst wall comparatively uniformly, and microballoon shows the susceptibility to temperature.The temperature-responsive magnetic microcapsules of this kind of special construction may be used for the height field such as target administration, spike, Co ntrolled release targetedly.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of temperature sensitive type anisotropic magnetic microcapsule
Fig. 2 is the TEM photo of temperature sensitive type anisotropic magnetic microcapsule
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Embodiment 1: the preparation of temperature sensitive type anisotropic magnetic microcapsule
Preparation massfraction is the sodium dodecyl sulfate aqueous solution of 0.05%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase; Be dispersed in by ferriferrous oxide nano-particle and be dissolved with in benzoyl peroxide, the hexanaphthene of hexadecanol, caprolactam, Vinylstyrene, vinylbenzene mixed solution, as oil phase, and the ultrasonic ferriferrous oxide nano-particle that makes is dispersed.Wherein benzoyl peroxide, ferriferrous oxide nano-particle, hexadecanol, hexanaphthene, caprolactam, Vinylstyrene, cinnamic quality are respectively 0.10g, 0.20g, 0.50g, 1.00g, 1.00g, 0.80g, 3.00g; Oil phase is joined in 80g aqueous phase, open and stir pre-emulsification 30min; System after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 15min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in; Under mechanical stirring, system temperature is risen to 80 DEG C, isothermal reaction 8h, be cooled to room temperature and obtain brown color emulsion; By obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Embodiment 2: the preparation of temperature sensitive type anisotropic magnetic microcapsule
Preparation massfraction is the sodium dodecyl benzene sulfonate aqueous solution of 0.5%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase; Be dispersed in by ferriferrous oxide nano-particle and be dissolved with in benzoyl peroxide, the normal heptane of hexadecanol, caprolactam, ethylene glycol dimethacrylate, vinylbenzene mixed solution, as oil phase, and the ultrasonic ferriferrous oxide nano-particle that makes is dispersed.Wherein benzoyl peroxide, ferriferrous oxide nano-particle, hexadecanol, normal heptane, caprolactam, ethylene glycol dimethacrylate, cinnamic quality are respectively 0.10g, 0.10g, 0.30g, 1.00g, 1.20g, 0.80g, 5.00g; Oil phase is joined in 100g aqueous phase, open and stir pre-emulsification 20min; System after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 15min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in; Under mechanical stirring, system temperature is risen to 90 DEG C, isothermal reaction 6h, be cooled to room temperature and obtain brown color emulsion; By obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Embodiment 3: the preparation of temperature sensitive type anisotropic magnetic microcapsule
Preparation massfraction is the sodium dodecyl benzene sulfonate aqueous solution of 0.5%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase; Ferriferrous oxide nano-particle is dispersed in and is dissolved with in Diisopropyl azodicarboxylate, the octane of paraffin, caprolactam, ethylene glycol dimethacrylate, glycidyl methacrylate mixed solution, as oil phase, and the ultrasonic ferriferrous oxide nano-particle that makes is dispersed.Wherein the quality of Diisopropyl azodicarboxylate, ferriferrous oxide nano-particle, paraffin, octane, caprolactam, ethylene glycol dimethacrylate, glycidyl methacrylate is respectively 0.10g, 0.50g, 0.30g, 1.00g, 1.50g, 0.80g, 3.00g; Oil phase is joined in 130g aqueous phase, open and stir pre-emulsification 20min; System after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 25min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in; Under mechanical stirring, system temperature is risen to 70 DEG C, isothermal reaction 12h, be cooled to room temperature and obtain brown color emulsion; By obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Embodiment 4: the preparation of temperature sensitive type anisotropic magnetic microcapsule
Preparation massfraction is the lauryl sodium sulfate aqueous solution of 0.35%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase; Ferriferrous oxide nano-particle is dispersed in and is dissolved with in benzoyl peroxide, the normal hexane of paraffin, caprolactam, ethylene glycol dimethacrylate, methyl methacrylate mixed solution, as oil phase, and the ultrasonic ferriferrous oxide nano-particle that makes is dispersed.Wherein the quality of benzoyl peroxide, ferriferrous oxide nano-particle, paraffin, normal hexane, caprolactam, ethylene glycol dimethacrylate, methyl methacrylate is respectively 0.10g, 0.30g, 0.60g, 1.30g, 1.00g, 0.80g, 4.00g; Oil phase is joined in 150g aqueous phase, open and stir pre-emulsification 10min; System after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 25min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in; Under mechanical stirring, system temperature is risen to 90 DEG C, isothermal reaction 9h, be cooled to room temperature and obtain brown color emulsion; By obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Embodiment 5: the preparation of temperature sensitive type anisotropic magnetic microcapsule
Preparation massfraction is the sodium dodecyl benzene sulfonate aqueous solution of 0.45%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase; Ferric oxide nanoparticles be dispersed in and be dissolved with in benzoyl peroxide, the normal heptane of paraffin, caprolactam, ethylene glycol dimethacrylate, vinylbenzene mixed solution, as oil phase, and the ultrasonic ferric oxide nanoparticles that makes is dispersed.Wherein benzoyl peroxide, ferric oxide nanoparticles, paraffin, normal heptane, caprolactam, ethylene glycol dimethacrylate, cinnamic quality are respectively 0.10g, 0.20g, 0.40g, 1.00g, 1.20g, 0.80g, 3.50g; Oil phase is joined in 110g aqueous phase, open and stir pre-emulsification 20min; System after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 15min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in; Under mechanical stirring, system temperature is risen to 90 DEG C, isothermal reaction 6h, be cooled to room temperature and obtain brown color emulsion; By obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Embodiment 6: the preparation of temperature sensitive type anisotropic magnetic microcapsule
Preparation massfraction is the sodium dodecyl benzene sulfonate aqueous solution of 0.15%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase; Ferric oxide nanoparticles be dispersed in and be dissolved with in Diisopropyl azodicarboxylate, the normal heptane of hexadecanol, caprolactam, Vinylstyrene, butyl methacrylate mixed solution, as oil phase, and the ultrasonic ferric oxide nanoparticles that makes is dispersed.Wherein the quality of Diisopropyl azodicarboxylate, ferric oxide nanoparticles, hexadecanol, normal heptane, caprolactam, Vinylstyrene, butyl methacrylate is respectively 0.10g, 0.10g, 0.50g, 0.80g, 1.20g, 0.90g, 3.00g; Oil phase is joined in 130g aqueous phase, open and stir pre-emulsification 20min; System after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 15min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in; Under mechanical stirring, system temperature is risen to 70 DEG C, isothermal reaction 9h, be cooled to room temperature and obtain brown color emulsion; By obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Embodiment 7: the preparation of temperature sensitive type anisotropic magnetic microcapsule
Preparation massfraction is the cetyl trimethylammonium bromide aqueous solution of 0.5%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase; Ferric oxide nanoparticles be dispersed in and be dissolved with in benzoyl peroxide, the Skellysolve A of paraffin, caprolactam, Vinylstyrene, vinylbenzene mixed solution, as oil phase, and the ultrasonic ferric oxide nanoparticles that makes is dispersed.Wherein benzoyl peroxide, ferric oxide nanoparticles, paraffin, Skellysolve A, caprolactam, Vinylstyrene, cinnamic quality are respectively 0.10g, 0.40g, 0.60g, 1.00g, 1.20g, 0.80g, 4.00g; Oil phase is joined in 160g aqueous phase, open and stir pre-emulsification 20min; System after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 30min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in; Under mechanical stirring, system temperature is risen to 80 DEG C, isothermal reaction 10h, be cooled to room temperature and obtain brown color emulsion; By obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Embodiment 8: the preparation of temperature sensitive type anisotropic magnetic microcapsule
Preparation massfraction is the sodium dodecyl benzene sulfonate aqueous solution of 0.4%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase; Ferric oxide nanoparticles is dispersed in and is dissolved with in Diisopropyl azodicarboxylate, the normal heptane of hexadecanol, caprolactam, ethylene glycol dimethacrylate, β-dimethyl-aminoethylmethacrylate mixed solution, as oil phase, and the ultrasonic ferric oxide nanoparticles that makes is dispersed.Wherein the quality of Diisopropyl azodicarboxylate, ferric oxide nanoparticles, hexadecanol, normal heptane, caprolactam, ethylene glycol dimethacrylate, β-dimethyl-aminoethylmethacrylate is respectively 0.10g, 0.50g, 0.70g, 1.50g, 1.20g, 1.80g, 3.00g; Oil phase is joined in 150g aqueous phase, open and stir pre-emulsification 20min; System after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 22min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in; Under mechanical stirring, system temperature is risen to 90 DEG C, isothermal reaction 7h, be cooled to room temperature and obtain brown color emulsion; By obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
Claims (6)
1. a preparation method for temperature sensitive type anisotropic magnetic microcapsule, is characterized in that step is as follows:
Step 1: preparation massfraction is the water phase surfactant mixture of 0.05% ~ 0.5%, inserts in the container that electric mixer, prolong and thermometer are housed as aqueous phase;
Step 2: be dispersed in by magnetic nano-particle in the monomer mixed solution being dissolved with initiator, assistant for emulsifying agent and capsule-core phase, as oil phase, carries out the ultrasonic magnetic nano-particle that makes to oil phase dispersed; The mass ratio of described initiator, magnetic nano-particle, assistant for emulsifying agent, capsule-core phase and monomer mixed solution is 1:1 ~ 5:3 ~ 8:5 ~ 15:30 ~ 100; Described monomer mixed solution is made up of caprolactam, linking agent, auxiliary monomer, and the mass ratio of three is 1:0.8 ~ 2.4:2 ~ 5; Described auxiliary monomer is: vinylbenzene, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate or glycidyl methacrylate;
Step 3: oil phase is joined in the container containing aqueous phase, the mass ratio of oil phase and aqueous phase is 1:10 ~ 25, opens and stirs pre-emulsification 10-30min;
Step 4: the system after pre-emulsification is inserted in ultrasonic cleaning machine, with the ultrasonic fine crankshaft 15-30min of 300W ultrasonic power, and then be transferred back to electric mixer, prolong and thermometer are housed container in;
Step 5: under mechanical stirring system temperature is risen to 70-90 DEG C, isothermal reaction 6-12h, is cooled to room temperature and obtains brown color emulsion;
Step 6: by obtained brown color emulsion through Magneto separate, wash, be drying to obtain temperature sensitive type anisotropic magnetic complex microsphere.
2. the preparation method of temperature sensitive type anisotropic magnetic microcapsule according to claim 1, is characterized in that: described tensio-active agent is: sodium laurylsulfonate, Sodium dodecylbenzene sulfonate, cetyl trimethylammonium bromide or sodium lauryl sulphate.
3. the preparation method of temperature sensitive type anisotropic magnetic microcapsule according to claim 1, is characterized in that: described magnetic nano-particle is: the nano ferriferrous oxide of surperficial oleic acid modified or ferric oxide.
4. the preparation method of temperature sensitive type anisotropic magnetic microcapsule according to claim 1, is characterized in that: described initiator is: benzoyl peroxide or Diisopropyl azodicarboxylate.
5. the preparation method of temperature sensitive type anisotropic magnetic microcapsule according to claim 1, is characterized in that: described assistant for emulsifying agent is: paraffin, Long carbon chain alkane or Long carbon chain aliphatics alcohols.
6. the preparation method of temperature sensitive type anisotropic magnetic microcapsule according to claim 1, is characterized in that: described capsule-core is mutually: normal hexane, hexanaphthene, normal heptane, octane or Skellysolve A.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107921181A (en) * | 2015-09-29 | 2018-04-17 | 上海氪励铵勤科技发展有限公司 | Application of the magnetic material in calculus taking-up |
| CN112980413A (en) * | 2021-03-05 | 2021-06-18 | 西南石油大学 | temperature/pH response type activator for filter cake scavenging solution in well cementation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1290604C (en) * | 2004-12-29 | 2006-12-20 | 浙江大学 | Process for preparing organic-inorganic hybrid nano microcapsule using polymer as core |
| CN100354039C (en) * | 2005-01-26 | 2007-12-12 | 浙江大学 | Preparation of organic-inorganic hybridized nanometer microcapsule with organic micromolecular hydrocarbon as model plate |
| CN100512945C (en) * | 2007-06-15 | 2009-07-15 | 浙江大学 | Method of preparing temperature sensitive nano microcapsule by using small molecule hydrocarbon as template |
| CN101862629B (en) * | 2010-06-17 | 2012-05-30 | 西北工业大学 | Method for preparing organic/inorganic composite magnetic microcapsules |
| CN101857699B (en) * | 2010-06-17 | 2011-08-24 | 西北工业大学 | Method for preparing organic-inorganic composite microspheres with eccentric structure |
| CN102125535B (en) * | 2011-01-24 | 2013-01-23 | 莆田学院 | Double-magnetic-response temperature-sensitive microcapsules and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107921181A (en) * | 2015-09-29 | 2018-04-17 | 上海氪励铵勤科技发展有限公司 | Application of the magnetic material in calculus taking-up |
| CN112980413A (en) * | 2021-03-05 | 2021-06-18 | 西南石油大学 | temperature/pH response type activator for filter cake scavenging solution in well cementation |
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