CN101070389A - Hollow micro-ball containing phosphazene and preparing method - Google Patents
Hollow micro-ball containing phosphazene and preparing method Download PDFInfo
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- CN101070389A CN101070389A CNA2007100423129A CN200710042312A CN101070389A CN 101070389 A CN101070389 A CN 101070389A CN A2007100423129 A CNA2007100423129 A CN A2007100423129A CN 200710042312 A CN200710042312 A CN 200710042312A CN 101070389 A CN101070389 A CN 101070389A
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- phosphine nitrile
- hexachlorocyclotriphosphazene
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Abstract
The present invention discloses a kind of phosphazenes-containing hollow microsphere as shown in the following figure, and its preparation method; specifically, the diameter of the hollow microsphere is 0.3-2.0mu m, and the internal hollow diameter of the hollow microsphere is 100-800 nm. The phosphazenes-containing hollow microsphere which has a body-type crosslinking structure, can be produced by crosslinking condensation reaction under the function of acid binding agent, and controllable hydrolysis, in sequence, between hexachlorocyclotriphosphazene and 4, 4'-dihydroxy diphenyl sulfone; the preparation method is novel, simple and feasible, which can be large scale prepared in industrial applications.The phosphazenes-containing hollow microsphere can be used in controlling drug release, efficient catalyst carriers, new photoelectric material, flame retardant materials, etc.
Description
Technical field:
The present invention relates to a kind of polymer microsphere and preparation method thereof, particularly a kind of phosphine nitrile tiny balloon and preparation method thereof that contains.
Background technology:
In recent years, various nano materials with special construction and special appearance have caused widely to be paid close attention to, and the tiny balloon structured material is one of them.Tiny balloon is to be developed by the core/shell composite structure material, can reach controllable adjustment by structure, size and the composition of regulating heterogeneous nuclear/shell composite particles, thereby realize cutting on a large scale its optics, calorifics, electricity, magnetics and catalytic property to its character.Because the material of this class formation has the characteristic of low density, high-ratio surface, and its hollow parts can hold a large amount of guest molecules or large-sized object, can produce some peculiar character, make the tiny balloon material important effect all be arranged in many technical fields such as medicine, biochemistry and chemical industry based on microcosmic " parcel " effect.And in recent years, containing the preparation of tiny balloon material of special chemical structure and simple preparation method's research is one of direction comparatively popular in this field.
What the preparation tiny balloon was the most frequently used is template, as utilizes PS, SiO
2Colloidal solid, the micro emulsion drop, polymer micelle after tensio-active agent vesica etc. make microballoon as template, promptly obtains tiny balloon [Dong AG, Micropor.Mesopor.Mater.64:69-81 (2003)] by removing template.Concrete preparation flow is: after making corresponding nuclear template, by of precipitation or the reaction of control presoma at the nuclear template surface, form surface coated core/shell structure, remove the nuclear template with the method for heating or chemical reaction again, promptly obtain hollow ball structure, the size of ball is by the size decision of template particles.The greatest problem for preparing the hollow ball existence of nanometer or micro-meter scale in this way is the specific template particles of needs preparation, and utilizes special means that template is removed at the last needs of reaction, has introduced the operation of a lot of inconvenience.
Except traditional template, utilize the method for self-assembly to prepare tiny balloon or vesica also is comparatively common means [Zhang LJ, Macromol.Rapid Commun.27:888-893 (2006)].Prepare microballoon by this method and do not need to add any template, and then not demand side to removing the problem of template difficulty, but this method need be synthesized the precursor with ad hoc structure, as has a hydrophilic and oleophilic group block polymer, this is often very difficult, therefore how to prepare suitable precursor, very big restriction the application of these class methods.
In addition, a lot of new technology had also been developed in recent years, as utilize the spray reaction legal system to be equipped with tiny balloon: its earlier with water, ethanol or other solvents with target presoma wiring solution-forming, again by spraying plant with solution atomization, atomized liquid forms drop through nozzle and enters in the reactor, and the solvent on drop surface evaporates rapidly, chemical reactions such as solute generation thermolysis or burning, precipitating forms a hollow ball shell, thereby has obtained the structure of hollow ball.Continuous, the formed product purity height of this method preparation process, size distribution is even, specific surface area is big, and composition, particle size and form are all controlled.But equipment that this method needs and reaction conditions require to have limited its further development than higher.
The tiny balloon that possesses biocompatibility and biodegradability is in biological medicine technology field great prospect, and especially the application in the medicament slow release system has caused a lot of scientific research personnel's attention.But the preparation method of the tiny balloon with biocompatibility and biodegradability of present report is relative complex, has limited its further research.
The phosphine nitrile compounds possesses particular performances, as the easy adjusting of chemically reactive and better biocompatibility and biodegradability, therefore has good potentiality to be used as the solid support material of controlled-release administrating system.So far, the preparation of relevant poly phosphazene polymer tiny balloon, vesica is as the application of the pharmaceutical carrier existing report of research [Allcock HR, Biomaromol.7:914-918 (2006)] with its drug release behavior, targeting.
Summary of the invention:
The object of the present invention is to provide a kind of have certain biocompatibility and a biodegradability contain phosphine nitrile tiny balloon, and overcome existing tiny balloon preparation method's shortcoming and defect, a kind of preparation method of simple environmental protection is provided.
A kind of chemical structure that contains phosphine nitrile tiny balloon of the present invention is shown below, and is a kind of build crosslinking structure:
Wherein containing phosphine nitrile tiny balloon diameter is 0.3～2.0 micron, and the boring diameter is the 100-800 nanometer.The present invention is a kind of, and to contain the preparation method of phosphine nitrile tiny balloon as follows:
With hexachlorocyclotriphosphazene and 4,4 '-dihydroxy diphenylsulphone is dissolved in the organic solvent, in reaction system, add acid binding agent again, wherein the concentration of hexachlorocyclotriphosphazene is 0.0001～0.1 grams per milliliter, hexachlorocyclotriphosphazene and 4, the mol ratio of 4 '-dihydroxy diphenylsulphone is 1: 3, and hexachlorocyclotriphosphazene and acid binding agent mol ratio are 1: 6; Under mechanical stirring, magnetic agitation or ultrasonication, under room temperature or reflux state, reacted 1 hour to 10 hours; Reaction finishes the back centrifugation, with organic solvent washing three times, with the aqueous solution that behind the deionized water wash three times product is placed pH value 1.0～13.0, under 20-95 ℃ of condition, stir and carried out controlled hydrolysis after promptly obtain containing phosphine nitrile tiny balloon after the centrifugation drying in 60-90 hour again.
The organic solvent that the present invention uses is tetrahydrofuran (THF), acetone, dioxane, ethanol, toluene or its mixture.
The acid binding agent that the present invention uses is triethylamine, pyridine, Anhydrous potassium carbonate or anhydrous sodium carbonate.
A kind of phosphine nitrile tiny balloon that contains of the present invention, its chemical structure be different from fully reported based on the high molecular microballoon of polyphosphonitrile; It at first utilizes hexachlorocyclotriphosphazene and 4, and 4 '-dihydroxy diphenylsulphone carries out crosslinked condensation reaction under the effect of acid binding agent, and then obtains the solid microsphere that internal structure is loose, surface tissue is fine and close; Again with this solid microsphere as in the aqueous solution, realize the controlled hydrolysis of internal loose structure by controlled temperature, pH value or reaction times, and then obtain having the tiny balloon of different hollow diameters.
A kind of phosphine nitrile tiny balloon that contains of the present invention, its boring diameter maximum can reach 800 nanometers, compares other polymer hollow microspheres and has bigger cavity structure; And its chemical structure belongs to the phosphine nitrile compounds, therefore has better biocompatibility and biodegradability; So this tiny balloon all potential playing an important role on many technical fields such as medicine, biochemistry.A kind of preparation method who contains phosphine nitrile tiny balloon of the present invention has utilized phosphazene compound unique biological degradability, by to the controlled hydrolysis of microballoon internal structure and then obtain tiny balloon.This method is different from the preparation method of all tiny balloons of having reported fully, it is advantageous that: not needing to add any special mould material just can obtain hollow structure by the degraded of self on the one hand, has avoided removing after the template problem of template difficulty; Do not need on the other hand synthetic anyly have the precursor of special construction and then avoided utilizing self-assembly method to prepare the problem of tiny balloon; Preparing microballoon in addition by this method is easy to realize to the requirement of experimental installation and experiment condition.
Description of drawings:
Fig. 1 is the field emission scanning electron microscope photo that contains phosphine nitrile tiny balloon of embodiment 1 gained,
Fig. 2 is the transmission electron microscope photo that contains phosphine nitrile tiny balloon of embodiment 1 gained,
Fig. 3 is the fourier-transform infrared spectrogram that contains phosphine nitrile tiny balloon of embodiment 1 gained,
Fig. 4 is the thermogravimetric curve (TGA) under the nitrogen atmosphere that contains phosphine nitrile tiny balloon of embodiment 1 gained.
Embodiment:
Embodiment 1:
In 500 ml flasks, with 0.5 gram (1.44 mmole) hexachlorocyclotriphosphazene and 1.08 gram (4.32 mmoles) 4,4 '-dihydroxy diphenylsulphone is dissolved in 250 milliliters of acetone, 0.87 gram (8.64 mmole) acid binding agent triethylamine is joined in the above-mentioned reaction system again; Under the 100w ultrasonication, reaction is 2 hours under room temperature.Reaction finishes the back and obtains white powder by centrifugation; With washing with acetone three times, be placed in the aqueous solution of pH value 7.0 with behind the deionized water wash three times again, under 80 ℃ of conditions, stir and carried out controlled hydrolysis after promptly obtain containing phosphine nitrile tiny balloon 0.82 gram after the centrifugation drying in 72 hours.
Fig. 1 is the field emission scanning electron microscope photo that contains phosphine nitrile tiny balloon of embodiment 1 gained, Fig. 2 is the transmission electron microscope photo that contains phosphine nitrile tiny balloon of embodiment 1 gained, containing phosphine nitrile tiny balloon diameter by Fig. 1 and visible this of Fig. 2 is 0.8～1.0 micron, and the boring diameter is the 300-400 nanometer.
Fig. 3 is the fourier-transform infrared spectrogram that contains phosphine nitrile tiny balloon of embodiment 1 gained, 1150cm
-1Bands of a spectrum are resonance absorption of P=N key, 1190cm
-1Bands of a spectrum are resonance absorption of P-O-Ar key, 1190
-1With 1290
-1Bands of a spectrum are resonance absorption of sulfuryl, and as seen its structure is hexachlorocyclotriphosphazene and 4, the crosslinked condensation structure of 4 '-dihydroxy diphenylsulphone.
Fig. 4 be embodiment 1 gained contain the thermogravimetric curve (TGA) of phosphine nitrile tiny balloon in nitrogen atmosphere, know that by figure the decomposition temperature under this microballoon nitrogen atmosphere is 521 ℃.
Embodiment 2:
In 500 ml flasks, with 0.5 gram (1.44 mmole) hexachlorocyclotriphosphazene and 1.08 gram (4.32 mmoles) 4,4 '-dihydroxy diphenylsulphone is dissolved in 250 milliliters of acetone, 0.87 gram (8.64 mmole) acid binding agent triethylamine is joined in the above-mentioned reaction system again; Under the magnetic agitation effect, reaction is 5 hours under room temperature.Reaction finishes the back and obtains white powder by centrifugation; With washing with acetone three times, be placed in the aqueous solution of pH value 7.0 with behind the deionized water wash three times again, under 80 ℃ of conditions, stir that to carry out controlled hydrolysis in 72 hours after centrifugation is dry centrifugal can obtain containing phosphine nitrile tiny balloon 0.86 gram.Electromicroscopic photograph shows that microballoon is that diameter is 1.0～1.2 microns, and the boring diameter is the 250-350 nanometer.Spectrum Analysis shows that its structure is hexachlorocyclotriphosphazene and 4, the crosslinked condensation structure of 4 '-dihydroxy diphenylsulphone.
Embodiment 3:
Adopt embodiment 1 described equipment and preparation process, just temperature of reaction is carried out under the reflux temperature of acetone, gets tiny balloon 0.85 gram.Interpretation shows that microballoon is that diameter is 1.3～1.5 microns, and the boring diameter is the 400-450 nanometer, and Spectrum Analysis shows that its structure is hexachlorocyclotriphosphazene and 4, the crosslinked condensation structure of 4 '-dihydroxy diphenylsulphone.
Embodiment 4:
Adopt embodiment 2 described equipment and preparation process, just reaction solvent is acetone and the mixed solvent of volume of toluene than 2: 1, obtains tiny balloon 0.74 gram.Electromicroscopic photograph shows that microballoon is that diameter is 0.7～0.8 micron, and the boring diameter is the 200-250 nanometer, and Spectrum Analysis shows that its structure is hexachlorocyclotriphosphazene and 4, the crosslinked condensation structure of 4 '-dihydroxy diphenylsulphone.
Claims (4)
1, a kind of phosphine nitrile tiny balloon that contains is characterized in that its chemical structure is shown below, and is a kind of build crosslinking structure:
Wherein phosphine nitrile tiny balloon diameter is 0.3～2.0 micron, and the boring diameter is the 100-800 nanometer.
2, a kind of preparation method who contains phosphine nitrile tiny balloon according to claim 1 is characterized in that the preparation method is as follows:
With hexachlorocyclotriphosphazene and 4,4 '-dihydroxy diphenylsulphone is dissolved in the organic solvent, in reaction system, add acid binding agent again, wherein the concentration of hexachlorocyclotriphosphazene is 0.0001～0.1 grams per milliliter, hexachlorocyclotriphosphazene and 4, the mol ratio of 4 '-dihydroxy diphenylsulphone is 1: 3, and hexachlorocyclotriphosphazene and acid binding agent mol ratio are 1: 6; Under mechanical stirring, magnetic agitation or ultrasonication, under room temperature or reflux state, reacted 1 hour to 10 hours; Reaction finishes the back centrifugation, with organic solvent washing three times, with the aqueous solution that behind the deionized water wash three times product is placed pH value 1.0～13.0, under 20-95 ℃ of condition, stir and carried out controlled hydrolysis after promptly obtain containing phosphine nitrile tiny balloon after the centrifugation drying in 60-90 hour again.
3, a kind of preparation method who contains phosphine nitrile tiny balloon according to claim 2 is characterized in that organic solvent is a tetrahydrofuran (THF), acetone, dioxane, ethanol, toluene or its mixture.
4, a kind of preparation method who contains the organic inorganic hybridization tiny balloon of phosphine nitrile according to claim 2 is characterized in that acid binding agent is triethylamine, pyridine, Anhydrous potassium carbonate or anhydrous sodium carbonate.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891936A (en) * | 2010-08-06 | 2010-11-24 | 上海交通大学 | Preparation method of composite material based on epoxy resin and phosphazene nanotubes |
| CN101875728B (en) * | 2009-11-12 | 2012-01-04 | 上海交通大学 | Polyphosphazene microsphere as well as preparation method, and application and implementation method thereof |
| CN102618054A (en) * | 2011-01-31 | 2012-08-01 | 韩财元 | Technology for increasing flame retardant performance of plastic by microbubbles |
| CN103694632A (en) * | 2013-11-27 | 2014-04-02 | 浙江工业大学之江学院工业研究院 | Preparation method of epoxy resin composite material |
| CN104327276A (en) * | 2014-09-15 | 2015-02-04 | 江南大学 | Cross-linking type polyphosphazene-based organic dye selective adsorbent and preparation method thereof |
| CN104628997A (en) * | 2015-02-10 | 2015-05-20 | 广东广山新材料有限公司 | Flame-retardant substance with bisphenol S group, flame-retardant epoxy resin and flame-retardant composition |
| CN105213218A (en) * | 2015-10-13 | 2016-01-06 | 上海交通大学 | Based on the ultraviolet absorber and preparation method thereof of phosphonitrilic polymer |
| CN106380604A (en) * | 2016-03-10 | 2017-02-08 | 中南大学 | Preparation method and application of polycyclotriphosphazen porous material |
| CN110204731A (en) * | 2019-05-27 | 2019-09-06 | 台州学院 | A kind of nanometer phosphonitrile microballoon and its preparation method and application containing ionic liquid |
| CN112774713A (en) * | 2021-01-25 | 2021-05-11 | 华南理工大学 | Bimetallic core-shell catalyst for electrocatalysis-synergetic hydrogen production and preparation method and application thereof |
| CN115010537A (en) * | 2022-05-06 | 2022-09-06 | 广州大丘有机农产有限公司 | Fermentation treatment process of agricultural and forestry waste |
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2007
- 2007-06-21 CN CNA2007100423129A patent/CN101070389A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875728B (en) * | 2009-11-12 | 2012-01-04 | 上海交通大学 | Polyphosphazene microsphere as well as preparation method, and application and implementation method thereof |
| CN101891936A (en) * | 2010-08-06 | 2010-11-24 | 上海交通大学 | Preparation method of composite material based on epoxy resin and phosphazene nanotubes |
| CN101891936B (en) * | 2010-08-06 | 2012-07-04 | 上海交通大学 | Preparation method of composite material based on epoxy resin and phosphazene nanotubes |
| CN102618054A (en) * | 2011-01-31 | 2012-08-01 | 韩财元 | Technology for increasing flame retardant performance of plastic by microbubbles |
| CN103694632A (en) * | 2013-11-27 | 2014-04-02 | 浙江工业大学之江学院工业研究院 | Preparation method of epoxy resin composite material |
| CN104327276A (en) * | 2014-09-15 | 2015-02-04 | 江南大学 | Cross-linking type polyphosphazene-based organic dye selective adsorbent and preparation method thereof |
| CN104628997A (en) * | 2015-02-10 | 2015-05-20 | 广东广山新材料有限公司 | Flame-retardant substance with bisphenol S group, flame-retardant epoxy resin and flame-retardant composition |
| CN105213218A (en) * | 2015-10-13 | 2016-01-06 | 上海交通大学 | Based on the ultraviolet absorber and preparation method thereof of phosphonitrilic polymer |
| CN105213218B (en) * | 2015-10-13 | 2018-01-02 | 上海交通大学 | Ultraviolet absorber based on phosphonitrilic polymer and preparation method thereof |
| CN106380604A (en) * | 2016-03-10 | 2017-02-08 | 中南大学 | Preparation method and application of polycyclotriphosphazen porous material |
| CN106380604B (en) * | 2016-03-10 | 2019-06-14 | 中南大学 | A kind of preparation method and its usage of polycyclic phosphine nitrile porous material |
| CN110204731A (en) * | 2019-05-27 | 2019-09-06 | 台州学院 | A kind of nanometer phosphonitrile microballoon and its preparation method and application containing ionic liquid |
| CN110204731B (en) * | 2019-05-27 | 2021-06-29 | 台州学院 | Nano phosphazene microsphere containing ionic liquid and preparation method and application thereof |
| CN112774713A (en) * | 2021-01-25 | 2021-05-11 | 华南理工大学 | Bimetallic core-shell catalyst for electrocatalysis-synergetic hydrogen production and preparation method and application thereof |
| CN115010537A (en) * | 2022-05-06 | 2022-09-06 | 广州大丘有机农产有限公司 | Fermentation treatment process of agricultural and forestry waste |
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