CN104072736A - Method for preparing conjugated polymer nano material - Google Patents
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- CN104072736A CN104072736A CN201410286876.7A CN201410286876A CN104072736A CN 104072736 A CN104072736 A CN 104072736A CN 201410286876 A CN201410286876 A CN 201410286876A CN 104072736 A CN104072736 A CN 104072736A
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Abstract
The invention provides a method for preparing a conjugated polymer nano material. The method comprises the following steps: dispersing anionic surfactant into a solvent to from micro emulsion; in the presence of oxidant, performing polymerization reaction on a polymer monomer in the micro emulsion by using a hydrothermal process, thereby obtaining the conjugated polymer nano material, wherein the anionic surfactant is sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfate and sulfo-sodium succinate dioctyl ester; the polymer monomer is 3,4-ethylenedioxythiophene, thiophene, pyrrole, phenylene vinylene, dopamine melanin and derivatives; the oxidant is FeCl3.6H2O, (NH4)2S2O8, copper acetate, H2O2 and AgNO3. The method adopts the anionic surfactant, the polymer monomer and the oxidant are locked in micelle of the anionic surfactant, and conjugated polymer nano particles which are controllable in form and size are stably synthesized through the hydrothermal process.
Description
Technical field
The invention belongs to field of nanometer material technology, also belong to organic synthesis field, be specifically related to a kind of preparation method of conjugated polymers nano material.
Background technology
Nano material is very important to future development biological, Material Field, and the breakthrough of many frontiers is supported in the urgent need to nano material and nanosecond science and technology, and the skill upgrading of conventional industries also has very large demand.The application of polymer nano material relates to every field, has a wide range of applications in machinery, electronics, optics, magnetics, chemistry and biology field.
The advantages such as conjugated polymers optical-thermal conversion material has that light abstraction width easily regulates and controls, uptake factor is high, cheap, good biocompatibility, the transform light energy of laser can be become to heat energy, realize localized hyperthermia, received widely and paid close attention to, obtained in recent years developing rapidly.The control of conjugated polymers nano material is synthesized and obtained significant progress in the photo-thermal therapy of tumour cell and mice with tumor model, and Chinese scholar is being made significant contribution aspect this.This class conjugated polymers nano material is widely used in biological field, need to possess: preparation method is simple, and cost is low and can stablize and synthesize the controlled nano material of pattern size.But, conventionally at room temperature, utilize the auxiliary polymer nano material pattern size being prepared into of tensio-active agent uncontrollable.For example, PEDOT nano particle (Yang, Y. have been prepared by traditional water-oil interface polymerization; Jiang, Y.; Xu, J.; Yu, J., Conducting polymeric nanoparticles synthesized in reverse micelles and their gas sensitivity based on quartz crystal micro balance.Polymer2007,48 (15), 4459-4465.), the polymer nano material pattern size that still this method obtains is difficult to control.
Summary of the invention
The object of the present invention is to provide a kind of method of preparing conjugated polymers nano material.
The method of preparing conjugated polymers nano material provided by the present invention, comprises the steps: anion surfactant to be scattered in solvent, forms micro emulsion; Under oxygenant exists, adopt hydrothermal method to make polymer monomer in described micro emulsion, carry out polyreaction, obtain described conjugated polymers nano material.
In aforesaid method, the anionic group in described anion surfactant be selected from following at least one: sulfate ion, sulfonate ion and phosphate anion.
Described anion surfactant specifically can be Sodium dodecylbenzene sulfonate (SDBS), sodium lauryl sulphate, sodium laurylsulfonate (SDS) or Dioctyl Sodium Sulfosuccinate (AOT) etc.
In aforesaid method, described solvent is selected from the mixed system of water or water and organic solvent composition; In the mixed system of described water and organic solvent composition, the volume ratio of water and organic solvent can be 1:1-3:1.
Described organic solvent is methyl alcohol or ethanol.
The proportioning of described anion surfactant and solvent is 0.2-2g:10-100mL.
Described oxygenant be selected from following at least one: FeCl
36H
2o, (NH
4)
2s
2o
8, CuAc (neutralized verdigris), H
2o
2and AgNO
3.
Described oxygenant adds with the form of solution, and the concentration of described oxidizing agent solution is 0.1-1M.
Described polymer monomer be selected from following any one: 3,4-ethylene dioxythiophene (EDOT), thiophene (Th), pyrroles (Py), aniline (ANI), phenylenevinylene, dopamine-melanin (Dpa-melanin) and derivative thereof.
The mol ratio of described anion surfactant and polymer monomer, oxygenant is followed successively by 2.5-5:1:1, is preferably 4:1:1.
According to the difference of the required polymerizing condition of described polymer monomer, in described polymerization reaction system, also can add sulfuric acid to regulate the pH value of described polymerization reaction system, as EDOT monomer, ANI monomer.
Described polyreaction is carried out in autoclave.
The condition (being hydrothermal condition) of described polyreaction is as follows: temperature is 120 DEG C-200 DEG C, and the time is 3h-24h; Optimum condition is: temperature is 140 DEG C, and the time is 5h.
Described method also comprises that the conjugated polymers nano material to obtaining washs and dry step.
Described washing solvent used be selected from following at least one: water and alcohol.Described washing can be carried out 2-6 time.
Described being dried as vacuum-drying, described vacuum drying temperature is 60 DEG C-100 DEG C, the time is 2-10h.
Described conjugated polymers nano material specifically can be conjugated polymers nano particle.
The present invention adopts anion surfactant, and polymer monomer and oxygenant are locked in anion surfactant micella, is stablized and has been synthesized the controlled conjugated polymers nano material of pattern size by hydrothermal method.
Brief description of the drawings
Fig. 1 is the transmission electron microscope photo of the PEDOT nano particle prepared of the embodiment of the present invention 1.
Fig. 2 is the infrared spectra of the PEDOT nano particle prepared of the embodiment of the present invention 1.
Fig. 3 is the UV spectrum of the PEDOT nano particle prepared of the embodiment of the present invention 1.
Fig. 4 is the transmission electron microscope photo of the PPy nano particle prepared of the embodiment of the present invention 2.
Fig. 5 is the UV spectrum of the PPy nano particle prepared of the embodiment of the present invention 2.
Fig. 6 is the transmission electron microscope photo of the PANI nano particle prepared of the embodiment of the present invention 3.
Fig. 7 is the transmission electron microscope photo of the PEDOT nano particle prepared of comparative example 1.
Fig. 8 is the electron scanning micrograph of the PEDOT nano particle in reference.
Fig. 9 is the transmission electron microscope photo of the PANI nano particle prepared of comparative example 2.
Embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
The experimental technique using in following embodiment if no special instructions, is ordinary method; Reagent, material etc. used in following embodiment, if no special instructions, all can obtain from commercial channels.
Embodiment 1, synthetic poly-3,4-ethylene dioxythiophene (PEDOT) nano particle of hydrothermal method
0.71 gram of (2.04mmol) SDBS, 10mL water, 10mL methyl alcohol and 10mL sulfuric acid (0.2M) are mixed, stir and obtain micro emulsion.In this solution, add EDOT (50 μ L, 0.47mmol) monomer, ultrasonic dispersion 10 minutes, stirs 20 minutes, adds subsequently and the equimolar FeCl of EDOT monomer again
36H
2in the aqueous solution of the water-soluble formation of O, stir 2 hours.Mixing solutions is transferred to 50mL water heating kettle, in 140 DEG C of hydrothermal treatment consists 5 hours.After naturally cooling, centrifugation goes out nano particle, uses methanol wash three times, dry.Can obtain PEDOT nano particle, its particle diameter is 15-20nm.These nano particles can well be dispersed in methyl alcohol.
Fig. 1 is the transmission electron microscope photo of the PEDOT nano particle for preparing.
Fig. 2 is the infrared spectra of the PEDOT nano particle for preparing.
Fig. 3 is the UV spectrum of the PEDOT nano particle for preparing.
As shown in Figure 1: the nano particle diameter that hydrothermal method makes is 15-20nm.
As shown in Figure 2: the nano particle that hydrothermal method makes is PEDOT.
As shown in Figure 3: the nano particle that hydrothermal method makes has absorption near infrared.
Embodiment 2, the synthetic poly-pyrrole of hydrothermal method are pressed against (PPy) nano particle
1.5 grams of (4.08mmol) SDBS, 10mL water are mixed, stir and obtain micro emulsion.Add Py (100 μ L, 1.44mmol) monomer at this solution, ultrasonic dispersion 10 minutes, stirs 20 minutes, adds subsequently and the equimolar FeCl of pyrrole monomer again
36H
2in the aqueous solution of the water-soluble formation of O, stir 2 hours.Mixing solutions is transferred to 50mL water heating kettle, in 140 DEG C of hydrothermal treatment consists 5 hours.After naturally cooling, centrifugation goes out nano material, uses washing with alcohol three times, dry.Can obtain PPy nano particle, its particle diameter is 20-30nm.These nano particles can well be dispersed in ethanol.
Fig. 4 is the transmission electron microscope photo of the PPy nano particle for preparing.
Fig. 5 is the UV spectrum of the PPy nano particle for preparing.
As shown in Figure 4: the nano particle diameter that hydrothermal method makes is 20-30nm.
As shown in Figure 5: the nano particle that hydrothermal method makes has absorption near infrared.
Embodiment 3, hydrothermal method synthesized polyaniline (PANI) nano particle
0.71 gram of (2.04mmol) SDS, 10mL water, 10mL methyl alcohol and 8mL sulfuric acid (0.2M) are mixed, stir and obtain micro emulsion.In this solution, add ANI (50 μ L, 0.55mmol) monomer, ultrasonic dispersion 10 minutes, stirs 20 minutes, adds subsequently and the equimolar (NH of ANI monomer again
4)
2s
2o
8in the aqueous solution of water-soluble formation, stir 2 hours.Mixing solutions is transferred to 50mL water heating kettle, in 140 DEG C of hydrothermal treatment consists 5 hours.After naturally cooling, centrifugation goes out nano material, uses methanol wash three times, dry.Can obtain PANI nano particle, its particle diameter is 10-25nm.These nano particles can well be dispersed in methyl alcohol.
Fig. 6 is the transmission electron microscope photo of the PANI nano particle for preparing.
As shown in Figure 6: the PANI nano particle diameter that hydrothermal method makes is 10-25nm.
Comparative example 1, prepare PEDOT nano particle by water-oil interface polymerization
According to reference Yang, Y.; Jiang, Y.; Xu, J.; Yu, J., Conducting polymeric nanoparticles synthesized in reverse micelles and their gas sensitivity based on quartz crystal micro balance.Polymer2007,48 (15), 4459-4465., prepares PEDOT nano particle by traditional water-oil interface polymerization.
Fig. 7 is the transmission electron microscope photo of the PEDOT nano particle for preparing.
As shown in Figure 7, the PEDOT nano particle preparing by described water-oil interface polymerization, its pattern is uncontrollable.
Fig. 8 is reference Yang, Y.; Jiang, Y.; Xu, J.; Yu, J., Conducting polymeric nanoparticles synthesized in reverse micelles and their gas sensitivity based on quartz crystal micro balance.Polymer2007,48 (15), the electron scanning micrograph of the disclosed PEDOT nano particle of preparing by water-oil interface polymerization of 4459-4465.
The result of Fig. 8 conforms to Fig. 7, and the PEDOT nano particle preparing by water-oil interface polymerization is all described, its pattern is uncontrollable.
Comparative example 2, prepare PANI nano particle by water-oil interface polymerization
According to reference Yang, Y.; Jiang, Y.; Xu, J.; Yu, J., Conducting polymeric nanoparticles synthesized in reverse micelles and their gas sensitivity based on quartz crystal micro balance.Polymer2007,48 (15), 4459-4465., prepares PANI nano particle by traditional water-oil interface polymerization.
Fig. 9 is the transmission electron microscope photo of the PANI nano particle for preparing.
Fig. 9 and Fig. 6 are contrasted known, the PANI nano particle preparing by described water-oil interface polymerization, its pattern is uncontrollable.
Claims (9)
1. prepare a method for conjugated polymers nano material, comprise the steps: anion surfactant to be scattered in solvent, form micro emulsion; Under oxygenant exists, adopt hydrothermal method to make polymer monomer in described micro emulsion, carry out polyreaction, obtain described conjugated polymers nano material.
2. method according to claim 1, is characterized in that: the anionic group in described anion surfactant be selected from following at least one: sulfate ion, sulfonate ion and phosphate anion.
3. method according to claim 1 and 2, is characterized in that: described anion surfactant be selected from following at least one: Sodium dodecylbenzene sulfonate, sodium lauryl sulphate and sodium laurylsulfonate or Dioctyl Sodium Sulfosuccinate.
4. according to the method described in any one in claim 1-3, it is characterized in that: described solvent be selected from following any one: the mixed system of water, water and organic solvent; In the mixed system of described water and organic solvent, the volume ratio of water and organic solvent is 1:1-3:1;
Described organic solvent is methyl alcohol or ethanol;
The proportioning of described anion surfactant and solvent is 0.2-2g:10-100mL.
5. according to the method described in any one in claim 1-4, it is characterized in that: described oxygenant be selected from following at least one: FeCl
36H
2o, (NH
4)
2s
2o
8, neutralized verdigris, H
2o
2and AgNO
3;
Described oxygenant adds with the form of solution, and the concentration of described oxidizing agent solution is 0.1-1M.
6. according to the method described in any one in claim 1-5, it is characterized in that: described polymer monomer be selected from following any one: 3,4-ethylene dioxythiophene, thiophene, pyrroles, aniline, phenylenevinylene, dopamine-melanin and derivative thereof;
The mol ratio of described anion surfactant and polymer monomer, oxygenant is followed successively by 2.5-5:1:1, is preferably 4:1:1.
7. according to the method described in any one in claim 1-6, it is characterized in that:
Described polyreaction is carried out in autoclave;
The condition of described polyreaction is as follows: temperature is 120 DEG C-200 DEG C, and the time is 3h-24h; Optimum condition is: temperature is 140 DEG C, and the time is 5h.
8. according to the method described in any one in claim 1-7, it is characterized in that: described method comprises that the conjugated polymers nano material to obtaining washs and dry step;
The solvent of described washing use be selected from following at least one: water and alcohol; Described washing is carried out 2-6 time;
Described being dried as vacuum-drying, described vacuum drying temperature is 60 DEG C-100 DEG C, the time is 2-10h.
9. according to the method described in any one in claim 1-8, it is characterized in that: described conjugated polymers nano material is conjugated polymers nano particle.
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| CN104479250A (en) * | 2014-12-18 | 2015-04-01 | 首都师范大学 | Multi-functional composite membrane with high photo-thermal conversion efficiency as well as preparation method and application of composite membrane |
| CN106893084A (en) * | 2017-03-03 | 2017-06-27 | 南昌大学 | A kind of dispersant makees the method that template in-situ polymerization prepares conducting polymer |
| CN107033332A (en) * | 2017-05-05 | 2017-08-11 | 浙江理工大学 | A kind of poly- 3,4 ethene dioxythiophene method for preparing Nano cube |
| CN109539613A (en) * | 2017-08-09 | 2019-03-29 | 首都师范大学 | Third biology window near infrared light is in the application as photothermal conversion excitation light source |
| CN110010369A (en) * | 2019-04-28 | 2019-07-12 | 福州大学 | One poly- 3,4- ethylenedioxy thiophene microballoon of type sea urchin shape and the preparation method and application thereof |
| CN110010368A (en) * | 2019-04-28 | 2019-07-12 | 福州大学 | A kind of poly- 3,4- ethylenedioxy thiophene of sheet and the preparation method and application thereof |
| CN111040135A (en) * | 2019-12-11 | 2020-04-21 | 复旦大学 | Conjugated polymer material with nuclear magnetic resonance imaging function and preparation method thereof |
| CN111072931A (en) * | 2019-06-03 | 2020-04-28 | 滨州职业学院 | PEDOT polymer and preparation method thereof |
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Cited By (12)
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| CN104479250A (en) * | 2014-12-18 | 2015-04-01 | 首都师范大学 | Multi-functional composite membrane with high photo-thermal conversion efficiency as well as preparation method and application of composite membrane |
| CN106893084A (en) * | 2017-03-03 | 2017-06-27 | 南昌大学 | A kind of dispersant makees the method that template in-situ polymerization prepares conducting polymer |
| CN107033332A (en) * | 2017-05-05 | 2017-08-11 | 浙江理工大学 | A kind of poly- 3,4 ethene dioxythiophene method for preparing Nano cube |
| CN109539613A (en) * | 2017-08-09 | 2019-03-29 | 首都师范大学 | Third biology window near infrared light is in the application as photothermal conversion excitation light source |
| CN109539613B (en) * | 2017-08-09 | 2020-11-10 | 首都师范大学 | Application of near-infrared light of third biological window as light-heat conversion excitation light source |
| CN110010369A (en) * | 2019-04-28 | 2019-07-12 | 福州大学 | One poly- 3,4- ethylenedioxy thiophene microballoon of type sea urchin shape and the preparation method and application thereof |
| CN110010368A (en) * | 2019-04-28 | 2019-07-12 | 福州大学 | A kind of poly- 3,4- ethylenedioxy thiophene of sheet and the preparation method and application thereof |
| CN110010369B (en) * | 2019-04-28 | 2020-09-01 | 福州大学 | Sea urchin-like poly 3, 4-ethylenedioxythiophene microspheres and preparation method and application thereof |
| CN111072931A (en) * | 2019-06-03 | 2020-04-28 | 滨州职业学院 | PEDOT polymer and preparation method thereof |
| CN111072931B (en) * | 2019-06-03 | 2022-08-26 | 滨州职业学院 | PEDOT polymer and preparation method thereof |
| CN111040135A (en) * | 2019-12-11 | 2020-04-21 | 复旦大学 | Conjugated polymer material with nuclear magnetic resonance imaging function and preparation method thereof |
| CN111040135B (en) * | 2019-12-11 | 2022-05-20 | 复旦大学 | Conjugated polymer material with nuclear magnetic resonance imaging function and preparation method thereof |
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