CN104072736B - A kind of preparation method of conjugated polymers nano material - Google Patents
A kind of preparation method of conjugated polymers nano material Download PDFInfo
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- CN104072736B CN104072736B CN201410286876.7A CN201410286876A CN104072736B CN 104072736 B CN104072736 B CN 104072736B CN 201410286876 A CN201410286876 A CN 201410286876A CN 104072736 B CN104072736 B CN 104072736B
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Abstract
The invention provides a kind of method preparing conjugated polymers nano material, comprise the steps: anion surfactant to be scattered in solvent, form micro emulsion; Under the effect of oxygenant, adopt hydrothermal method to make polymer monomer carry out polyreaction in described micro emulsion, obtain described conjugated polymers nano material.Described anion surfactant is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate and Dioctyl Sodium Sulfosuccinate, described polymer monomer is 3,4-ethylenedioxy thiophene, thiophene, pyrroles, aniline, phenylenevinylene, dopamine-melanin and derivative thereof, described oxygenant is FeCl
36H
2o, (NH
4)
2s
2o
8, neutralized verdigris, H
2o
2and AgNO
3.The present invention adopts anion surfactant, polymer monomer and oxygenant is locked in anion surfactant micella, is stablized synthesized the controlled conjugated polymers nano particle of pattern size by hydrothermal method.
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 that is biological, Material Field, and the breakthrough of many frontiers supports 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 heat energy, realize localized hyperthermia, have received and pay close attention to widely, obtain in recent years and develop rapidly.The control synthesis of conjugated polymers nano material and achieve significant progress in the photo-thermal therapy of tumour cell and tumor mouse model, Chinese scholar has made significant contribution in this.This kind of conjugated polymers nano material is widely used in biological field, needs to possess: preparation method is simple, and cost is low and can stablize and synthesize the controlled nano material of pattern size.But usually at room temperature, the polymer nano material pattern size utilizing tensio-active agent to assist to be prepared into is uncontrollable.Such as, PEDOT nano particle (Yang, Y. has been prepared by traditional water-oil interface polymerization; Jiang, Y.; Xu, J.; Yu, J., Conductingpolymericnanoparticlessynthesizedinreversemice llesandtheirgassensitivitybasedonquartzcrystalmicrobalan ce.Polymer2007,48 (15), 4459-4465.), but the polymer nano material pattern size that this method obtains be difficult to control.
Summary of the invention
The object of the present invention is to provide a kind of method preparing conjugated polymers nano material.
The method preparing conjugated polymers nano material provided by the present invention, comprises the steps: anion surfactant to be scattered in solvent, forms micro emulsion; In the presence of an oxidizer, adopt hydrothermal method to make polymer monomer carry out polyreaction in described micro emulsion, obtain described conjugated polymers nano material.
In aforesaid method, the anionic group in described anion surfactant is 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 is 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 as a 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.
The difference of polymerizing condition needed for 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 (i.e. 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 carries out washing and dry step to the conjugated polymers nano material obtained.
Described washing solvent used is selected from following at least one: water and alcohol.Described washing can be carried out 2-6 time.
Described drying is vacuum-drying, and described vacuum drying temperature is 60 DEG C-100 DEG C, and the time is 2-10h.
Described conjugated polymers nano material specifically can be conjugated polymers nano particle.
The present invention adopts anion surfactant, polymer monomer and oxygenant is locked in anion surfactant micella, is stablized synthesized the controlled conjugated polymers nano material of pattern size by hydrothermal method.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of PEDOT nano particle prepared by the embodiment of the present invention 1.
Fig. 2 is the infrared spectra of PEDOT nano particle prepared by the embodiment of the present invention 1.
Fig. 3 is the UV spectrum of PEDOT nano particle prepared by the embodiment of the present invention 1.
Fig. 4 is the transmission electron microscope photo of PPy nano particle prepared by the embodiment of the present invention 2.
Fig. 5 is the UV spectrum of PPy nano particle prepared by the embodiment of the present invention 2.
Fig. 6 is the transmission electron microscope photo of PANI nano particle prepared by the embodiment of the present invention 3.
Fig. 7 is the transmission electron microscope photo of PEDOT nano particle prepared by 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 PANI nano particle prepared by 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 used in following embodiment if no special instructions, is ordinary method; Reagent used in following embodiment, material etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1, water heat transfer gather 3,4-ethylene dioxythiophene (PEDOT) nano particle
0.71 gram of (2.04mmol) SDBS, 10mL water, 10mL methyl alcohol and 10mL sulfuric acid (0.2M) are mixed, stirs and obtain micro emulsion.In this solution, add EDOT (50 μ L, 0.47mmol) monomer, ultrasonic disperse 10 minutes, stir 20 minutes, add FeCl equimolar with EDOT monomer subsequently 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, by 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 prepared.
Fig. 2 is the infrared spectra of the PEDOT nano particle prepared.
Fig. 3 is the UV spectrum of the PEDOT nano particle prepared.
As shown in Figure 1: the nano particle diameter that hydrothermal method obtains is 15-20nm.
As shown in Figure 2: the nano particle that hydrothermal method obtains is PEDOT.
As shown in Figure 3: the nano particle that hydrothermal method obtains has absorption near infrared.
Embodiment 2, water heat transfer gather pyrrole and press against (PPy) nano particle
1.5 grams of (4.08mmol) SDBS, 10mL water are mixed, stirs and obtain micro emulsion.Add Py (100 μ L, 1.44mmol) monomer at this solution, ultrasonic disperse 10 minutes, stir 20 minutes, add with pyrrole monomer equimolar FeCl subsequently 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, by washing with alcohol three times, dry.Can obtain PPy nano particle, its particle diameter is 20-30nm.These nano particles can well disperse in ethanol.
Fig. 4 is the transmission electron microscope photo of the PPy nano particle prepared.
Fig. 5 is the UV spectrum of the PPy nano particle prepared.
As shown in Figure 4: the nano particle diameter that hydrothermal method obtains is 20-30nm.
As shown in Figure 5: the nano particle that hydrothermal method obtains has absorption near infrared.
Embodiment 3, water heat transfer polyaniline (PANI) nano particle
0.71 gram of (2.04mmol) SDS, 10mL water, 10mL methyl alcohol and 8mL sulfuric acid (0.2M) are mixed, stirs and obtain micro emulsion.In this solution, add ANI (50 μ L, 0.55mmol) monomer, ultrasonic disperse 10 minutes, stir 20 minutes, add (NH equimolar with ANI monomer subsequently 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, by 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 prepared.
As shown in Figure 6: the PANI nano particle diameter that hydrothermal method obtains 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., Conductingpolymericnanoparticlessynthesizedinreversemice llesandtheirgassensitivitybasedonquartzcrystalmicrobalan ce.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 prepared.
As shown in Figure 7, the PEDOT nano particle prepared by described water-oil interface polymerization, its pattern is uncontrollable.
Fig. 8 is reference Yang, Y.; Jiang, Y.; Xu, J.; Yu, J., Conductingpolymericnanoparticlessynthesizedinreversemice llesandtheirgassensitivitybasedonquartzcrystalmicrobalan ce.Polymer2007, the electron scanning micrograph of 48 (15), the 4459-4465 disclosed PEDOT nano particles prepared by water-oil interface polymerization.
The result of Fig. 8 conforms to Fig. 7, and the PEDOT nano particle prepared 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., Conductingpolymericnanoparticlessynthesizedinreversemice llesandtheirgassensitivitybasedonquartzcrystalmicrobalan ce.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 prepared.
Contrasted by Fig. 9 and Fig. 6 known, the PANI nano particle prepared by described water-oil interface polymerization, its pattern is uncontrollable.
Claims (7)
1. prepare a method for conjugated polymers nano material, comprise the steps: anion surfactant to be scattered in solvent, form micro emulsion; In the presence of an oxidizer, adopt hydrothermal method to make polymer monomer carry out polyreaction in described micro emulsion, obtain described conjugated polymers nano material;
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;
Described anion surfactant is selected from following at least one: Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium laurylsulfonate and Dioctyl Sodium Sulfosuccinate;
Described conjugated polymers nano material is conjugated polymers nano particle.
2. method according to claim 1, is characterized in that: described oxygenant is selected from following at least one: FeCl
36H
2o, (NH
4)
2s
2o
8, neutralized verdigris, H
2o
2and AgNO
3;
Described oxygenant adds as a solution, and the concentration of described oxidizing agent solution is 0.1-1M.
3. method according to claim 1, 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.
4. method according to claim 3, is characterized in that: the mol ratio of described anion surfactant and polymer monomer, oxygenant is followed successively by 4:1:1.
5. method according to claim 1, 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.
6. method according to claim 5, is characterized in that: the condition of described polyreaction is as follows: temperature is 140 DEG C, and the time is 5h.
7. method according to claim 1, is characterized in that: described method comprises carries out washing and dry step to the conjugated polymers nano material obtained;
The solvent of described washing is selected from following at least one: water and alcohol; Described washing is carried out 2-6 time;
Described drying is vacuum-drying, and described vacuum drying temperature is 60 DEG C-100 DEG C, and the time is 2-10h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104479250B (en) * | 2014-12-18 | 2016-11-09 | 首都师范大学 | A kind of multifunctional composite film with high photo-thermal conversion efficiency and preparation method and application |
| CN106893084B (en) * | 2017-03-03 | 2019-04-12 | 南昌大学 | A kind of dispersing agent 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 |
| 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 |
| 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 |
| CN111072931B (en) * | 2019-06-03 | 2022-08-26 | 滨州职业学院 | PEDOT polymer 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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