CN103214670A - Aqueous polyaniline hollow microballoon and preparation method thereof - Google Patents
Aqueous polyaniline hollow microballoon and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an aqueous polyaniline hollow microballoon and preparation method thereof, which belongs to the field of the polyaniline material technology, and solves the technical problem that the polyaniline hollow microballoon in prior art can not be dissolved in water, and only dissolves in a poisonous and harmful volatile organic solvent when used with environment pollution. The preparation method of the aqueous polyaniline hollow microballoon includes the following steps: a step a), dissolving aniline and sulfonic aniline in water and obtaining an aqueous dispersion liquid; a step b), dissolving potassium ferricyanide in water and obtaining a potassium ferricyanide aqueous solution; a step c) mixing the aqueous dispersion liquid and the potassium ferricyanide aqueous solution for reaction, and obtaining the reaction products by filtering; a step d), drying the obtained reaction products from the step c), and obtaining the aqueous polyaniline hollow microballoon. The preparation method of the present invention has the advantages of simple method and low cost, and the prepared aqueous polyaniline hollow microballoon has excellent water dispersability, and can be dissolved in water for obtaining an aqueous polyaniline solution.
Description
Technical field
The present invention relates to the polyaniline material technical field, more particularly, relate to a kind of aqueous polyanion hollow microsphere and preparation method thereof.
Background technology
The polyaniline hollow microsphere is with a wide range of applications in fields such as the noenergy loss transmission of biology, medicine etc., controlled separation and release, the protections of artificial cell nuclear bioactive ingredients owing to its special hollow structure.Simultaneously, the high-specific surface area of polyaniline hollow microsphere, low permeability and density make that it is synthetic at microreactor, biosensor, pigment, have a wide range of applications on the energy storage.The preparation method of several polyaniline hollow microspheres is disclosed in the prior art, as: people such as Wan Meixiang (Adv.Mater., 2007,19 (16): 2092) with the Perfluorooctane sulfonates be doping agent, iron trichloride is an oxygenant, the diameter that has prepared imitative rambutan structure is that 385nm and wall thickness are the hollow polyaniline microsphere of 35nm, this electrically conductive polyaniline tiny balloon shows excellent ultra-hydrophobicity, not only improve the stability of electrically conductive polyaniline electric conductivity, and can also protect the not contaminated and destructions such as biomaterial in the cavity; With the ammonium persulphate is oxygenant, and Whitfield's ointment is a doping agent, and having prepared diameter is polyaniline hollow microsphere (Adv.Funct.Mater., 2003,13 (10): 815 of 1.5-3.1 μ m; With the beta-naphthalenesulfonic-acid is doping agent, and having prepared diameter is polyaniline hollow microsphere (Adv.Mater., 2002,14 (18): 1314) of 450-1370nm.But, in the above-mentioned document, along with the carrying out of aniline polymerization reaction about preparation polyaniline hollow microsphere, the pH value of reaction system reduces, and in order to stop micella transformation toward patterns such as other linearities from spherical, all needs to add materials such as doping agent, therefore, complicated operation, cost is higher.
For addressing the above problem, Chinese patent 201110040481.5 discloses a kind of without any need for doping agent, and having prepared diameter with the oxygenant of suboxide reduction potential is 160-610nm, and wall thickness is the polyaniline hollow microsphere of 65-100nm.But the polyaniline hollow microsphere of above-mentioned patent is the solvent-borne type polyaniline, can not be dissolved in the water, must be dissolved in the poisonous and harmful volatile organic solvent and just can use, and its application is restricted, and can cause huge pollution to environment.
Summary of the invention
Water insoluble for solving in the prior art polyaniline hollow microsphere, can only be dissolved in the technical problem of contaminate environment in the poisonous and harmful volatile organic solvent during use, the invention provides a kind of aqueous polyanion hollow microsphere and preparation method thereof, this preparation method is simple, cost is low, and the aqueous polyanion hollow microsphere that obtains has excellent water dispersible.
The invention provides a kind of preparation method of aqueous polyanion hollow microsphere, may further comprise the steps:
Step a) is dissolved in aniline and sulfo aniline in the water, obtains aqueous liquid dispersion;
Step b) is dissolved in the Tripotassium iron hexacyanide in the water, obtains potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and reaction obtains reaction product after filtration;
Step d) obtains the aqueous polyanion hollow microsphere with the reaction product drying that step c) obtains.
Preferably, the consumption of described aniline is 95 weight parts, and the consumption of sulfo aniline is the 87-118 weight part, and the consumption of the Tripotassium iron hexacyanide is the 481-3290 weight part.
Preferably, the mass percentage concentration of aniline is 21.2%-31.5% in the described aqueous liquid dispersion, and the mass percentage concentration of sulfo aniline is 20.9%-35.4%.
Preferably, the mass percentage concentration of the Tripotassium iron hexacyanide is 53.2%-82.9% in the described potassium ferricyanide aqueous solution.
Preferably, described sulfo aniline is 2-aniline sulfonic acid, 3-aniline sulfonic acid or 4-acetylaminohydroxyphenylarsonic acid 2-aniline sulfonic acid.
Preferably, the described temperature of reaction of step c) is-20～15 ℃, and the reaction times is 20～48 hours.
Preferably, the described drying of step d) is vacuum-drying 24～72 hours.
Preferably, also comprise, use methyl alcohol, water and methanol wash successively before the described reaction product drying of step c).
The present invention also provides the aqueous polyanion hollow microsphere of above-mentioned preparation method's preparation.
Preferably, the diameter of described aqueous polyanion hollow microsphere is 300～600nm, and wall thickness is 50～68nm.
Beneficial effect of the present invention:
(1) the present invention is oxygenant with the Tripotassium iron hexacyanide, serves as the raw material for preparing the polyaniline hollow microsphere with aniline with containing sulfonic aniline, in preparation process, amino in the aniline and the amino in the sulfo aniline and sulfonic group are hydrophilic radical, phenyl ring in the aniline and the phenyl ring in the sulfo aniline are hydrophobic group, thereby, aniline and sulfo aniline are the amphiphilic group compound, in water, can form spherical micelle, carrying out along with the aniline polymerization reaction, the Tripotassium iron hexacyanide of suboxide reduction potential E=1.8V makes the pH value of reaction system significantly not reduce, stoped the formation of linear polyaniline pattern, guaranteed the formation of polyaniline hollow microsphere, the sulfonic group in the sulfo aniline has excellent wetting ability, has guaranteed that the aqueous polyanion hollow microsphere that obtains can be dissolved in the water well;
(2) preparation method of the present invention does not add any doping agent, and technology is simple, cost is low;
(3) diameter of the prepared aqueous polyanion hollow microsphere of the present invention is 300～600nm, wall thickness is 50～68nm, and has good water dispersible, can be dissolved in and obtain aqueous polyanion solution in the water, overcome the technical problem that need be dissolved in when the polyaniline hollow microsphere uses in the prior art in the poisonous and harmful volatile organic solvent, environmental protection.
Description of drawings
Fig. 1 is the scanning electron microscope picture and the deployment conditions of this polyaniline hollow microsphere in water of the polyaniline hollow microsphere of Comparative Examples 1 preparation of the present invention;
Fig. 2 is the scanning electron microscope picture and the deployment conditions of this aqueous polyanion hollow microsphere in water of the aqueous polyanion hollow microsphere of the embodiment of the invention 1 preparation;
Fig. 3 is the GPC spectrogram of the aqueous polyanion hollow microsphere of the embodiment of the invention 1 preparation;
Fig. 4 is the scanning electron microscope picture and the deployment conditions of this aqueous polyanion hollow microsphere in water of the aqueous polyanion hollow microsphere of the embodiment of the invention 2 preparations;
Fig. 5 is the GPC spectrogram of the aqueous polyanion hollow microsphere of the embodiment of the invention 2 preparations.
Embodiment
The preparation method of aqueous polyanion hollow microsphere may further comprise the steps:
Step a) is dissolved in aniline and sulfo aniline in the water, obtains aqueous liquid dispersion;
Step b) is dissolved in the Tripotassium iron hexacyanide in the water, obtains potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and reaction obtains reaction product after filtration;
Step d) obtains the aqueous polyanion hollow microsphere with the reaction product drying that step c) obtains.
Among the preparation method of the present invention, the consumption of preferred described aniline is 95 weight parts, and the consumption of sulfo aniline is the 87-118 weight part, and the consumption of the Tripotassium iron hexacyanide is the 481-3290 weight part.
Among the preparation method of the present invention, the mass percentage concentration of aniline is 21.2%-31.5% in the preferred described aqueous liquid dispersion, and the mass percentage concentration of sulfo aniline is 20.9%-35.4%.
Among the preparation method of the present invention, the mass percentage concentration of the Tripotassium iron hexacyanide is preferably 53.2%-82.9% in the described potassium ferricyanide aqueous solution.
Among the preparation method of the present invention, described sulfo aniline is preferably 2-aniline sulfonic acid, 3-aniline sulfonic acid or 4-acetylaminohydroxyphenylarsonic acid 2-aniline sulfonic acid.
Among the preparation method of the present invention, the temperature of the described reaction of step c) is preferably-20～15 ℃, is more preferably-5～5 ℃, and the reaction times is preferably 20～48 hours, is more preferably 24-36 hour.
Among the preparation method of the present invention, the described drying of step d) was preferably vacuum-drying 24～72 hours, was more preferably vacuum-drying 30～40 hours; Described vacuum tightness is 0.06～0.09MPa, is more preferably 0.07～0.08MPa; Drying temperature is preferably 40～55 ℃, is more preferably 45～50 ℃.
Preparation method of the present invention preferably also comprises, the described reaction product of step c) is used methyl alcohol, water and methanol wash successively before drying.
As preferred version, the preparation method of aqueous polyanion hollow microsphere is:
Step a) is dissolved in the aniline of 95 weight parts and the sulfo aniline of 87-118 weight part in the water of 120-235 weight part, obtains aqueous liquid dispersion;
Step b) is dissolved the Tripotassium iron hexacyanide of 1481-3290 weight part in the 680-1300 weight parts water, obtain potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and under-20～15 ℃ of temperature, static placement 20～48 hours then, is filtered, and it is colourless to wash filtrate successively with methyl alcohol, water, methyl alcohol, obtains reaction product;
Step d) obtains the aqueous polyanion hollow microsphere with reaction product vacuum-drying 24～72 hours.
The present invention also provides the aqueous polyanion hollow microsphere of above-mentioned preparation method's preparation, and the diameter of aqueous polyanion hollow microsphere is 300～600nm, and wall thickness is 50～68nm.
In order to further specify the present invention, technical scheme of the present invention is done further explanation below in conjunction with embodiment and accompanying drawing.
Comparative Examples 1
In conjunction with Fig. 1 Comparative Examples 1 is described
The preparation method of polyaniline hollow microsphere:
Step a) is dissolved in 135g aniline in the water of 180ml, obtains aqueous liquid dispersion;
Step b) is dissolved the Tripotassium iron hexacyanide of 1481g in 680ml water, obtain potassium ferricyanide aqueous solution;
Step c) is mixed the solution that step a) and step b) obtain, and under-20 ℃ of temperature, static placement 20 hours then, is filtered, and it is colourless to wash filtrate successively with methyl alcohol, water, methyl alcohol, obtains reaction product;
Step d) obtains the polyaniline hollow microsphere with reaction product vacuum-drying 24 hours.
Fig. 1 is the scanning electron microscope picture and the deployment conditions of this polyaniline hollow microsphere in water of the polyaniline hollow microsphere of Comparative Examples 1 preparation of the present invention; Fig. 1 a is the scanning electron microscope picture of polyaniline hollow microsphere, and Fig. 1 b is the deployment conditions of polyaniline hollow microsphere in water; As can be seen from Figure 1: the polyaniline hollow microsphere of prior art for preparing does not dissolve in water, can be clear that demixing phenomenon, is water layer above, is polyaniline powder below, and promptly the polyaniline hollow microsphere is deposited in aqueous solution bottom.
Embodiment 1
In conjunction with Fig. 2 and Fig. 3 embodiment 1 is described
The preparation of aqueous polyanion hollow microsphere:
Step a) is dissolved in the 2-aniline sulfonic acid of 95g aniline and 87g in the water of 120ml, obtains aqueous liquid dispersion;
Step b) is dissolved the Tripotassium iron hexacyanide of 1481g in 680ml water, obtain potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and under-20 ℃ of temperature, static placement 20 hours then, is filtered, and it is colourless to wash filtrate successively with methyl alcohol, water, methyl alcohol, obtains reaction product;
Step d) obtains the aqueous polyanion hollow microsphere with reaction product vacuum-drying 24 hours.
Fig. 2 is the scanning electron microscope picture and the deployment conditions of this aqueous polyanion hollow microsphere in water of the aqueous polyanion hollow microsphere of the embodiment of the invention 1 preparation; Fig. 2 a is the scanning electron microscope picture of aqueous polyanion hollow microsphere, and Fig. 2 b is the deployment conditions of aqueous polyanion hollow microsphere in water; As can be seen from Figure 2: the diameter of the aqueous polyanion hollow microsphere of the embodiment of the invention 1 preparation is 300～580nm, and wall thickness is 55～68nm, the dispersion that it can be good in water, and solution is black.
Fig. 3 is the GPC spectrogram of the aqueous polyanion hollow microsphere of the embodiment of the invention 1 preparation; As can be seen from Figure 3, the Z-average molecular weight (Mz) of the aqueous polyanion hollow microsphere of the embodiment of the invention 1 is 345835, M
Z+1Be 1177284, weight-average molecular weight (Mw) is 102267, and number-average molecular weight (Mn) is 20829, and peak molecular weight (Mp) is 85711.
Embodiment 2
In conjunction with Fig. 4 and Fig. 5 embodiment 2 is described
The preparation of aqueous polyanion hollow microsphere:
Step a) is dissolved in the aniline of 95g and the 4-acetylaminohydroxyphenylarsonic acid 2-aniline sulfonic acid of 118g in the water of 235ml, obtains aqueous liquid dispersion;
Step b) is dissolved the Tripotassium iron hexacyanide of 3290g in 1300ml water, obtain potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and under 15 ℃ of temperature, static placement 48 hours then, is filtered, and it is colourless to wash filtrate successively with methyl alcohol, water, methyl alcohol, obtains reaction product;
Step d) obtains the aqueous polyanion hollow microsphere with reaction product vacuum-drying 72 hours.
Fig. 4 is the scanning electron microscope picture and the deployment conditions of this aqueous polyanion hollow microsphere in water of the aqueous polyanion hollow microsphere of the embodiment of the invention 2 preparations; Fig. 4 a is the scanning electron microscope picture of aqueous polyanion hollow microsphere, and Fig. 4 b is the deployment conditions of aqueous polyanion hollow microsphere in water; As can be seen from Figure 2: the diameter of the aqueous polyanion hollow microsphere of the embodiment of the invention 2 preparations is 380～600nm, and wall thickness is 50～62nm, the dispersion that it can be good in water, and solution is black.
Fig. 5 is the GPC spectrogram of the aqueous polyanion hollow microsphere of the embodiment of the invention 2 preparations; As can be seen from Figure 5, the Z-average molecular weight (Mz) of the aqueous polyanion hollow microsphere of the embodiment of the invention 5 is 295884, M
Z+1Be 702186, weight-average molecular weight (Mw) is 108484, and number-average molecular weight (Mn) is 23972, and peak molecular weight (Mp) is 105726.
Embodiment 3
The preparation of aqueous polyanion hollow microsphere:
Step a) is dissolved in the 3-aniline sulfonic acid of 95g aniline and 92g in the water of 180ml, obtains aqueous liquid dispersion;
Step b) is dissolved the Tripotassium iron hexacyanide of 1680g in 1100ml water, obtain potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and under-10 ℃ of temperature, static placement 36 hours then, is filtered, and it is colourless to wash filtrate successively with methyl alcohol, water, methyl alcohol, obtains reaction product;
Step d) obtains the aqueous polyanion hollow microsphere with reaction product vacuum-drying 48 hours, and microsphere diameter is 340～510nm, and wall thickness is 58～63nm.
Embodiment 4
The preparation of aqueous polyanion hollow microsphere:
Step a) is dissolved in the aniline of 95g and the 2-aniline sulfonic acid of 102g in the water of 200ml, obtains aqueous liquid dispersion;
Step b) is dissolved the Tripotassium iron hexacyanide of 2860g in 780ml water, obtain potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and under 5 ℃ of temperature, static placement 24 hours then, is filtered, and it is colourless to wash filtrate successively with methyl alcohol, water, methyl alcohol, obtains reaction product;
Step d) obtains the aqueous polyanion hollow microsphere with reaction product vacuum-drying 60 hours, and microsphere diameter is 310～480nm, and wall thickness is 52～60nm.
Embodiment 5
The preparation of aqueous polyanion hollow microsphere:
Step a) is dissolved in the aniline of 95g and the 3-aniline sulfonic acid of 115g in the water of 165ml, obtains aqueous liquid dispersion;
Step b) is dissolved the Tripotassium iron hexacyanide of 3290g in 1200ml water, obtain potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and under-5 ℃ of temperature, static placement 38 hours then, is filtered, and it is colourless to wash filtrate successively with methyl alcohol, water, methyl alcohol, obtains reaction product;
Step d) obtains the aqueous polyanion hollow microsphere with reaction product vacuum-drying 36 hours, and microsphere diameter is 330～520nm, and wall thickness is 54～62nm.
The explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof.Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention, can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. the preparation method of aqueous polyanion hollow microsphere is characterized in that, may further comprise the steps:
Step a) is dissolved in aniline and sulfo aniline in the water, obtains aqueous liquid dispersion;
Step b) is dissolved in the Tripotassium iron hexacyanide in the water, obtains potassium ferricyanide aqueous solution;
Step c) is mixed aqueous liquid dispersion and potassium ferricyanide aqueous solution, and reaction obtains reaction product after filtration;
Step d) obtains the aqueous polyanion hollow microsphere with the reaction product drying that step c) obtains.
2. the preparation method of aqueous polyanion hollow microsphere according to claim 1 is characterized in that, the consumption of described aniline is 95 weight parts, and the consumption of sulfo aniline is the 87-118 weight part, and the consumption of the Tripotassium iron hexacyanide is the 481-3290 weight part.
3. the preparation method of aqueous polyanion hollow microsphere according to claim 1 is characterized in that, the mass percentage concentration of aniline is 21.2%-31.5% in the described aqueous liquid dispersion, and the mass percentage concentration of sulfo aniline is 20.9%-35.4%.
4. the preparation method of aqueous polyanion hollow microsphere according to claim 1 is characterized in that, the mass percentage concentration of the Tripotassium iron hexacyanide is 53.2%-82.9% in the described potassium ferricyanide aqueous solution.
5. the preparation method of aqueous polyanion hollow microsphere according to claim 1 is characterized in that, described sulfo aniline is 2-aniline sulfonic acid, 3-aniline sulfonic acid or 4-acetylaminohydroxyphenylarsonic acid 2-aniline sulfonic acid.
6. the preparation method of aqueous polyanion hollow microsphere according to claim 1 is characterized in that, the described temperature of reaction of step c) is-20～15 ℃, and the reaction times is 20～48 hours.
7. the preparation method of aqueous polyanion hollow microsphere according to claim 1 is characterized in that, the described drying of step d) is vacuum-drying 24～72 hours.
8. the preparation method of aqueous polyanion hollow microsphere according to claim 1 is characterized in that, also comprises, the described reaction product of step c) is used methyl alcohol, water and methanol wash successively before drying.
9. the aqueous polyanion hollow microsphere of the preparation method of any one described aqueous polyanion hollow microsphere of claim 1-8 preparation.
10. aqueous polyanion hollow microsphere according to claim 9 is characterized in that, described diameter of micro ball is 300～600nm, and wall thickness is 50～68nm.
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| CN103539943A (en) * | 2013-11-06 | 2014-01-29 | 中国科学院长春应用化学研究所 | Preparation method of polyaniline |
| CN104629585A (en) * | 2015-02-03 | 2015-05-20 | 中南大学 | Anticorrosive paint taking rare earth cerium ion modified polyaniline hollow microspheres as additive |
| CN105017551A (en) * | 2014-04-22 | 2015-11-04 | 中国石油化工股份有限公司 | Surface modified polymer hollow microsphere as well as preparation method and application thereof |
| CN105778085A (en) * | 2016-03-28 | 2016-07-20 | 重庆金固特新材料科技有限公司 | Preparation method for polyaniline |
| CN107591540A (en) * | 2017-08-27 | 2018-01-16 | 长沙小新新能源科技有限公司 | A kind of preparation method of biological fuel cell anode material |
| CN110639438A (en) * | 2019-08-16 | 2020-01-03 | 华东理工大学 | Preparation of polyaniline hollow microspheres and method for recycling precious metals in electronic waste |
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