CN103113410A - High-temperature resistant polyphosphazene microsphere and preparation method thereof - Google Patents
High-temperature resistant polyphosphazene microsphere and preparation method thereof Download PDFInfo
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- CN103113410A CN103113410A CN2013100688604A CN201310068860A CN103113410A CN 103113410 A CN103113410 A CN 103113410A CN 2013100688604 A CN2013100688604 A CN 2013100688604A CN 201310068860 A CN201310068860 A CN 201310068860A CN 103113410 A CN103113410 A CN 103113410A
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Abstract
The invention relates to a high-temperature resistant polyphosphazene microsphere and a preparation method thereof and belongs to the organic micro-nanometer filed. The method comprises the following steps: performing reaction among hexachlorocyclopentadiene, phloroglucinol and triethylamine in an ultrasonic water bath environment to obtain a product; and washing the product, thereby obtaining the high-temperature resistant polyphosphazene microsphere. The high-temperature resistant polyphosphazene microsphere has a chemical structural formula shown in the specification. According to the microsphere and the method provided by the invention, the defects of the existing polymer microsphere preparation method and the existing polymer performance are overcome. Therefore, the polymer microsphere with better performance is synthetized by utilizing a simpler method.
Description
Technical field
What the present invention relates to is the material in a kind of organic micro-nano field and preparation method thereof, specifically a kind of high temperature resistant poly (organophosphazenes) microsphere and preparation method thereof.
Background technology
In recent years, along with nanotechnology research deepen continuously and to the continuous expansion of every field, and the excellent properties of poly phosphazene material, the poly phosphazene material with micro nano structure has obtained scientific research personnel's concern day by day.Micro-nano poly phosphazene material combines the character that the high-specific surface area of micro Nano material is easy to organic decoration, has obtained the micro Nano material of some excellent performances.
The micro polymer ball material is used very extensive, as plastics additive, and coating, sizing agent, material of construction etc.In recent years, micro-nano micro polymer ball material demonstrates the application in the high-end technology field gradually, solid electrolyte material for example, mould material, drug delivery controlled release system, microreactor, liquid crystal material, chromatographic column packing material etc.Prepare the method for polymer microsphere take monomer as raw material mainly by letex polymerization, emulsifier-free emulsion polymerization, suspension polymerization, microemulsion, mini-emulsion polymerization, SPG film emulsion polymerization, seeding polymerization, dispersion polymerization, precipitation polymerization etc., but the suitable method for preparing cross-linked polymer microsphere only has seeding polymerization, SPG film emulsion polymerization and precipitation polymerization etc., wherein precipitation polymerization does not need to add the stablizers such as tensio-active agent, the 2nd, the elasticity by rigid microspheres in polymerization process guarantees that they are not inter-adhesive, and then obtains the polymer microballoon of stable uniform.
The poly phosphazene micro Nano material is based on the micro Nano material of the organic inorganic hybridization of the class novelty that ring cross-linking type poly phosphazene obtains, the poly phosphazene micro Nano material has different patterns, its component units is mainly organic composition, with various macromolecular materials, good consistency and avidity are arranged, with respect to inorganic nano material, a lot of superiority is arranged.And the poly phosphazene micro Nano material also possesses the advantage of the easy chemical modification of poly phosphazene material, can obtain by simple nucleophilic substitution reaction surface of various chemical property etc.
Since Allcock synthesizes solvable polydichlorophosphazene in nineteen sixty-five, poly phosphazene has been widely used in solid electrolyte material, fire retardant material, nonlinear optical material, separation membrane material, biomaterial etc., Allcock etc. utilize the hydrogel of poly phosphazene polyelectrolyte to prepare the microcapsule that are used for medicine control release, connect hydrophilic radicals such as carboxylic phenol on the side chain of poly phosphazene, the form crosslinked with ionization forms hydrogel, after the protein such as coating vaccine, can be made into microcapsule membrane material etc.At first nearest Nicole L.Morozowich etc. has reported synthetic (Macromolecules, (2011)) of the poly phosphazene that comprises vitamin b6 usp side group group, can evoke cell response, has good application prospect in organizational project is used.
At present existing a large amount of linear, grafting and crosslinked poly phosphazene material are synthesized, and crosslinked poly (organophosphazenes) microsphere is still comparatively single, wherein the patent of Zhu Lu etc. discloses the synthetic of a kind of crosslinking poly (organophosphazenes) microsphere, but wherein contain a large amount of weak bonds, cause its thermal characteristics can not satisfy the weakness such as application of some high temperature occasion.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of high temperature resistant poly (organophosphazenes) microsphere and preparation method thereof is proposed, overcome the shortcoming and defect of existing method for preparing polymer micro and polymer performance, synthesize the better polymer microballoon of performance by more simple method.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of high temperature resistant poly (organophosphazenes) microsphere, its chemical structural formula is shown below:
The present invention relates to the preparation method of above-mentioned crosslinking poly (organophosphazenes) microsphere, by obtaining after the product washing that reaction under hexachlorocyclotriphosphazene, Phloroglucinol and triethylamine ultrasonic water bath environment is obtained.
The concentration of described hexachlorocyclotriphosphazene is preferably 0.1～5g/L, and the mol ratio of hexachlorocyclotriphosphazene and Phloroglucinol is preferably 1:1～1:3, and the mol ratio of hexachlorocyclotriphosphazene and triethylamine is preferably 1:6～1:16.
Described ultrasonic water bath refers to: be 10～60 ℃ in temperature, power is in the ultrasonic water bath of 50～190W, reacts 1 minute to 3 hours.
Described washing refers to: with product organic solvent washing three times, then use deionized water wash three times, namely get crosslinking poly (organophosphazenes) microsphere after drying.
Described organic solvent is acetonitrile.
Crosslinking poly (organophosphazenes) microsphere of the present invention has the chemical structure by hexachlorocyclotriphosphazene and the crosslinked condensation of Phloroglucinol, under nitrogen atmosphere record 800 ℃ the time residual rate be about 70%, have good thermostability.Crosslinking poly (organophosphazenes) microsphere of the present invention is that single stage method is completed, and simple process is easily gone, can preparation in a large number in industrial application.This crosslinking poly (organophosphazenes) microsphere can be applicable to: efficient catalytic agent carrier, fire retardant material, chromatographic column packing material, the control of medicine and release etc.
Description of drawings
Fig. 1 is the transmission electron microscope photo of crosslinking poly (organophosphazenes) microsphere.
Fig. 2 is the stereoscan photograph of crosslinking poly (organophosphazenes) microsphere.
Fig. 3 is the field emission scanning electron microscope photo of crosslinking poly (organophosphazenes) microsphere.
Fig. 4 is the Fourier transform infrared spectroscopy figure of crosslinking poly (organophosphazenes) microsphere.
Fig. 5 is the thermogravimetric curve (TGA) of crosslinking poly (organophosphazenes) microsphere under nitrogen atmosphere.
Embodiment
The below elaborates to embodiments of the invention, and the present embodiment is implemented under take technical solution of the present invention as prerequisite, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Add 0.06 gram (0.18 mmole) hexachlorocyclotriphosphazene in the 100mL flask, 0.04 gram (0.36 mmole) Phloroglucinol, add 50mL acetonitrile dispersing and dissolving, add 2 milliliters of (1.44 mmole) triethylamines when bath temperature reaches 30 ℃, react 3h in ultrasonic (190W) water bath with thermostatic control, after reaction finishes, solid is through centrifugation, with crude product washing with alcohol three times, then use deionized water wash three times, dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.
Fig. 1 is the transmission electron microscope photo of gained crosslinking poly (organophosphazenes) microsphere, Fig. 2 is the stereoscan photograph of crosslinking poly (organophosphazenes) microsphere, Fig. 3 is the field emission scanning electron microscope photo of crosslinking poly (organophosphazenes) microsphere, is about 800nm by the diameter of visible this microballoon of photo, and microsphere surface is smooth is solid construction.
Fig. 4 is the Fourier transform infrared spectrogram of crosslinking poly (organophosphazenes) microsphere, and in figure, 1 and 2 is resonance absorption of phenyl ring, the resonance absorption of the 3rd, P=N key, and the resonance absorption of the 4th, P-O-Ar key, the 5th, unreacted is the resonance absorption of hydroxyl completely.
Fig. 5 is the thermogravimetric curve of crosslinking poly (organophosphazenes) microsphere in nitrogen atmosphere, knows that by figure the decomposition temperature under nitrogen atmosphere is 450 ℃, and in the time of 800 ℃, remaining rate is about 70%.
Embodiment 2
Adopt the described equipment of embodiment 1 and preparation process, hexachlorocyclotriphosphazene is 0.06 gram (0.18 mmole), Phloroglucinol is 0.06 gram (0.54 mmole), with crude product washing with alcohol three times, then use deionized water wash three times, dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.Interpretation shows, the diameter of microballoon is about 800nm, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 3
Adopt the described equipment of embodiment 1 and preparation process, ultrasonic power used is 190W, the water bath with thermostatic control temperature is 30 ℃, takes out sample segment when the reaction times is respectively 1min, 10min, 30min, 1h, 2h, 3h, through ethanol and deionized water wash repeatedly after sample preparation.The SEM interpretation shows, the diameter of microballoon is 800nm～900nm, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 4
Add 0.026 gram (0.075 mmole) hexachlorocyclotriphosphazene in the 100mL flask, 0.019 gram (0.15 mmole) Phloroglucinol, add 50mL acetonitrile dispersing and dissolving, add 1.5 milliliters of (1 mmole) triethylamines when bath temperature reaches 40 ℃, react 3h in ultrasonic (150W) water bath with thermostatic control, after reaction finishes, solid is through centrifugation, with crude product washing with alcohol three times, then use deionized water wash three times, dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.The SEM interpretation shows, the diameter of microballoon is about 650nm, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Adopt equipment and the preparation process shown in embodiment 4, hexachlorocyclotriphosphazene used is 0.06 gram (0.18 mmole), Phloroglucinol is the 0.04(0.36 mmole), triethylamine is 2mL (1.44 mmole), with crude product washing with alcohol three times, then use deionized water wash three times, dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.The SEM interpretation shows, the diameter of microballoon is about 800nm, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 6
Adopt equipment and the preparation process shown in embodiment 4, hexachlorocyclotriphosphazene used is 0.12 gram (0.36 mmole), Phloroglucinol is the 0.08(0.72 mmole), triethylamine is 2mL (1.44 mmole), with crude product washing with alcohol three times, then use deionized water wash three times, dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.The SEM interpretation shows, the diameter of microballoon is about 1000nm, and microspherulite diameter is slightly inhomogeneous, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 7
Adopt equipment and the preparation process shown in embodiment 4, hexachlorocyclotriphosphazene used is 0.25 gram (0.72 mmole), Phloroglucinol is 0.16 gram (1.44 mmole), triethylamine is 4mL (2.88 mmole), with crude product washing with alcohol three times, then use deionized water wash three times, dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.The SEM interpretation shows, the diameter of microballoon is about 1100nm, and microspherulite diameter is slightly inhomogeneous, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 8
Adopt the described equipment of embodiment 1 and preparation process, ultrasonic power used is 50W, and the water bath with thermostatic control temperature is 40 ℃, with crude product washing with alcohol three times, then uses deionized water wash three times, and dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.Interpretation shows, the diameter of microballoon is about 800nm, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 9
Adopt the described equipment of embodiment 1 and preparation process, ultrasonic power used is 150W, and the water bath with thermostatic control temperature is 40 ℃, with crude product washing with alcohol three times, then uses deionized water wash three times, and dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.Interpretation shows, the diameter of microballoon is about 850nm, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 10
Adopt the described equipment of embodiment 1 and preparation process, the water bath with thermostatic control temperature is 40 ℃, with crude product washing with alcohol three times, then uses deionized water wash three times, and dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.Interpretation shows, the diameter of microballoon is about 800nm, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Embodiment 11
Adopt the described equipment of embodiment 1 and preparation process, the water bath with thermostatic control temperature is 60 ℃, with crude product washing with alcohol three times, then uses deionized water wash three times, and dry 24h namely gets crosslinking poly (organophosphazenes) microsphere in vacuum drying oven at last.Interpretation shows, the diameter of microballoon is about 900nm, and microspherulite diameter is inhomogeneous, and more adhesion is arranged, and microsphere surface is smooth is solid construction, and its structure is the crosslinked condensation structure of hexachlorocyclotriphosphazene and Phloroglucinol.
Claims (10)
1. a high temperature resistant poly (organophosphazenes) microsphere, is characterized in that, its chemical structural formula is shown below:
2. the preparation method of crosslinking poly (organophosphazenes) microsphere according to claim 1, is characterized in that, by obtaining after the product washing that reaction under hexachlorocyclotriphosphazene, Phloroglucinol and triethylamine ultrasonic water bath environment is obtained.
3. method according to claim 2, is characterized in that, the concentration of described hexachlorocyclotriphosphazene is 0.1～5g/L, and the mol ratio of hexachlorocyclotriphosphazene and Phloroglucinol is 1:1～1:3, and the mol ratio of hexachlorocyclotriphosphazene and triethylamine is 1:6～1:16.
4. method according to claim 2, is characterized in that, described ultrasonic water bath refers to: be 10～60 ℃ in temperature, power is in the ultrasonic water bath of 50～190W, reacts 1 minute to 3 hours.
5. method according to claim 2, is characterized in that, described washing refers to: with product organic solvent washing three times, then use deionized water wash three times, namely get crosslinking poly (organophosphazenes) microsphere after drying.
6. method according to claim 2, is characterized in that, described organic solvent is acetonitrile.
7. according to claim 2 or 3 described methods, it is characterized in that, the consumption of described hexachlorocyclotriphosphazene is 0.18mmol, and the consumption of Phloroglucinol is 0.36mmol～0.54mmol, and described triethylamine consumption is 1.44 mmoles and adds when bath temperature reaches 30 ℃.
8. according to claim 2 or 3 described methods, it is characterized in that, the consumption of described hexachlorocyclotriphosphazene is 0.075-0.72mmol, and the consumption of Phloroglucinol is 0.15mmol～1.44mmol, and described triethylamine consumption is the 1-2.88 mmole and adds when bath temperature reaches 0 ℃.
9. according to claim 2 or 4 described methods, is characterized in that, described ultrasonic power is 50W, 150W or 190W.
10. according to claim 2 or 4 described methods, is characterized in that, the temperature of described water-bath is 30 ℃, 40 ℃ or 60 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626804A (en) * | 2013-11-25 | 2014-03-12 | 上海交通大学 | Polyphosphazene microspheres containing resveratrol units and preparation method thereof |
| CN104497316A (en) * | 2014-12-10 | 2015-04-08 | 上海交通大学 | High-nitrogen-content polymeric microsphere and preparation method thereof |
| CN107400242A (en) * | 2017-07-29 | 2017-11-28 | 福州大学 | A kind of preparation method of Synthesis, Characterization of Polyphosphazenes microballoon |
| CN110031447A (en) * | 2019-05-13 | 2019-07-19 | 福州大学 | A kind of detection method that substrate being immunized using magnetic surface enhancing Raman |
| CN113122045A (en) * | 2021-04-16 | 2021-07-16 | 安徽中铁工程材料科技有限公司 | Polymer latex interface stabilizer, emulsified asphalt waterproof coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560227A (en) * | 2009-05-26 | 2009-10-21 | 瓮福（集团）有限责任公司 | Flame-retarding compound, flame-retardant prepared thereby and preparation method thereof |
| CN101659677A (en) * | 2009-09-17 | 2010-03-03 | 上海交通大学 | Triphosphazene epoxy resin and preparation method thereof |
| CN101993456A (en) * | 2010-10-14 | 2011-03-30 | 北京工商大学 | Method for preparing phosphaphenanthrene and phosphazene halogen-free retardant agent |
-
2013
- 2013-03-05 CN CN2013100688604A patent/CN103113410A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560227A (en) * | 2009-05-26 | 2009-10-21 | 瓮福（集团）有限责任公司 | Flame-retarding compound, flame-retardant prepared thereby and preparation method thereof |
| CN101659677A (en) * | 2009-09-17 | 2010-03-03 | 上海交通大学 | Triphosphazene epoxy resin and preparation method thereof |
| CN101993456A (en) * | 2010-10-14 | 2011-03-30 | 北京工商大学 | Method for preparing phosphaphenanthrene and phosphazene halogen-free retardant agent |
Non-Patent Citations (2)
| Title |
|---|
| TINGJUN PAN ET AL.: "Controlled Fabrication of Uniform Hollow Bowl-Shaped Microspheres Based on Polyphosphazene Material", 《MACROMOL. CHEM. PHYS》 * |
| TINGJUN PAN ET AL.: "Intrinsically Fluorescent Microspheres with Superior Thermal Stability and Broad Ultraviolet-Visible Absorption Based on Hybrid Polyphosphazene Material", 《MACROMOL. CHEM. PHYS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626804A (en) * | 2013-11-25 | 2014-03-12 | 上海交通大学 | Polyphosphazene microspheres containing resveratrol units and preparation method thereof |
| CN103626804B (en) * | 2013-11-25 | 2016-04-27 | 上海交通大学 | Polyphosphazene microspheres containing trans-resveratrol unit and preparation method thereof |
| CN104497316A (en) * | 2014-12-10 | 2015-04-08 | 上海交通大学 | High-nitrogen-content polymeric microsphere and preparation method thereof |
| CN107400242A (en) * | 2017-07-29 | 2017-11-28 | 福州大学 | A kind of preparation method of Synthesis, Characterization of Polyphosphazenes microballoon |
| CN110031447A (en) * | 2019-05-13 | 2019-07-19 | 福州大学 | A kind of detection method that substrate being immunized using magnetic surface enhancing Raman |
| CN113122045A (en) * | 2021-04-16 | 2021-07-16 | 安徽中铁工程材料科技有限公司 | Polymer latex interface stabilizer, emulsified asphalt waterproof coating and preparation method thereof |
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Application publication date: 20130522 |