CN104629071A - Preparation method of polyaniline hollow microspheres with rare earth cerium ions loaded on surfaces - Google Patents
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Abstract
The invention discloses a preparation method of polyaniline hollow microspheres with rare earth cerium ions loaded on the surfaces. The method is prepared by rapidly adding an ammonium persulfate solution in a mixed solution consisting of poly (2-acrylamide-2-methylpro panesulfonic acid), aniline, ethanol and water to react, so that after the reaction is completed, polyaniline hollow microspheres are obtained; and putting the obtained polyaniline hollow microspheres in a cerous nitrate (III) solution, and carrying out stirring and doping, so that polyaniline hollow microspheres with rare earth cerium ions loaded on the surfaces are obtained. The prepared polyaniline hollow microspheres with rare earth cerium ions loaded on the surfaces are neat in structure, regular in morphology, large in specific surface area, and high in electric conductivity, and the preparation method is simple, efficient, and easy to control, therefore, the method is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of hollow polyaniline microspheres of area load rare-earth cerium ion, belong to functional polymer field of compound material.
Background technology
Polyaniline is a kind of important conductive polymers.Synthesize easy, environmental stability good, electroconductibility high makes it show huge application potential in fields such as semiconductor material, battery, ultracapacitor, electromagnetic shielding material, corrosion protection coatings.At present, the polyaniline (as polyaniline nano fiber, polyaniline microsphere, polyaniline nanotube etc.) of multiple different shape is developed.In the polyaniline of these different shapes, the polyaniline microsphere of hollow structure shows considerable application potential in biomedical devices, drug release, coating additive, the field such as to be separated due to the structure of its uniqueness.The existing method preparing hollow polyaniline mainly contains template and self-assembly method.Wherein self-assembly method needs to remove external template after the completion of reaction, and the properity of the polyaniline of preparation all can be affected.Self-assembly method is the more method of Recent study, people (the Polymer such as Zhang Hongming, 2011,52:4246-4252) particle size distribution range that adopted self assembling process to prepare is the hollow polyaniline microspheres of 380nm-700nm, but the microballoon specific conductivity of preparation is only 1.3 × 10
-3s/cm.The people such as M.Ghorbani (Polymer, 2013,54:5586-5594) have also prepared hollow polyaniline microsphere by self-assembly method, but the diameter range of the microballoon of preparation comparatively large (about 2.5 μm).In addition, some patents (Chinese patent: 201310069386.7 in recent years; Chinese patent: 201110040481.5) also relate to hollow polyaniline microspheres, but the reagent using prussiate or other environmental pollution in preparation process, greatly limit its application.Therefore, develop easy, efficient, eco-friendly method prepare high conductivity, narrower particle diameter hollow polyaniline microspheres necessary.
Steel corrosion is the major issue be concerned always, and therefore people also have employed diverse ways to prevent the generation of corrosion.Wherein, the inhibiter containing chromium has significant preservative effect, but chromic salts is containing toxic and carinogenicity, and this also greatly limit its application.At present, have and report that cerium salt can as inhibiter, be applied to different metals and alloy anticorrosion, there is the characteristics such as efficient, nontoxic, environmental friendliness, but the area load not for steel anti-corrosive in prior art has the report of the polymer microballoon of rare-earth cerium ion.
Summary of the invention
Method existence for the hollow polyaniline microspheres prepared in prior art is unfriendly to environment, efficiency is low, and the defect such as obtained hollow polyaniline microspheres particle diameter is comparatively large, conductivity is poor, preservative effect is not good, the object of the invention is to be to provide a kind of, for steel and alloy rot-resistant, there is compound with regular structure, pattern rule, specific surface area area load that is large, electric conductivity high have the method for the hollow polyaniline microspheres of rare-earth cerium ion, the method is easy, efficient, easy to control, is applicable to suitability for industrialized production.
The invention provides the preparation method that a kind of area load has the hollow polyaniline microspheres of rare-earth cerium ion, the method is by poly-(2-acrylamide-2-methylpro panesulfonic acid), aniline, ammonium persulfate solution is added fast in the mixing solutions of second alcohol and water composition, first react at 50 ~ 80 DEG C of temperature, react further at 0 ~ 5 DEG C of temperature again, after having reacted, obtain hollow polyaniline microspheres, gained hollow polyaniline microspheres be placed in cerous nitrate (III) solution stir at 25 ~ 50 DEG C of temperature doping after, obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.
Area load of the present invention has the preparation method of the hollow polyaniline microspheres of rare-earth cerium ion also to comprise following preferred version:
In preferred scheme, mixing solutions is made up of following mass percent component: poly-(2-acrylamide-2-methylpro panesulfonic acid) 0.5 ~ 4.9%, aniline 2.2 ~ 2.5%, ethanol 7.4 ~ 7.8%, water 84.8 ~ 89.9%.
In preferred scheme, cerous nitrate (III) solution quality percentage concentration is 0.057 ~ 2.79%.
The time of reacting at 50 ~ 80 DEG C of temperature in preferred scheme is 1 ~ 2min.
In preferred scheme, at 0 ~ 5 DEG C of temperature, the time of reaction is further 4 ~ 12h.
The time of stirring doping in preferred scheme is 4 ~ 12h.
Further preferred scheme: (2-acrylamide-2-methylpro panesulfonic acid) will be gathered and aniline joins in ethanol/water mixed solvent, mix, obtain mixing solutions, the mass percent of mixing solutions consists of: poly-(2-acrylamide-2-methylpro panesulfonic acid) 0.5 ~ 4.9%, aniline 2.2 ~ 2.5%, ethanol 7.4 ~ 7.8%, water 84.8 ~ 89.9%; After gained mixed solution is warming up to 50 ~ 80 DEG C, add the ammonium persulfate aqueous solution that temperature is 50 ~ 80 DEG C fast, after holding temperature reaction 1 ~ 2min, adjust the temperature to 0 ~ 5 DEG C of reaction 4 ~ 12h further immediately; Breakdown of emulsion, washing, the hollow polyaniline microspheres obtained; Gained hollow polyaniline microspheres is placed in cerous nitrate (III) solution that mass percent concentration is 0.057 ~ 2.79%, doping 4 ~ 12h is stirred at 25 ~ 50 DEG C of temperature, suction filtration, washing, drying, obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.
In preferred scheme, the concentration of ammonium persulfate aqueous solution is 0.057 ~ 0.171g/mL; The add-on of ammonium persulphate is 0.8 ~ 1.2 times of aniline moles.
The area load that the present invention obtains has the hollow polyaniline microspheres of rare-earth cerium ion to can be used as corrosion protection coating additive application in steel anti-corrosive.Specifically there is by area load the hollow polyaniline microspheres of rare-earth cerium ion to be added in iron and steel coating formula, prepare corrosion protection coating at steel surface, improve steel anti-corrosive performance.Iron and steel coating formula comprises following component: epoxy resin E-51 or E-44, dimethylbenzene, propyl carbinol, flow agent BYK-306 and polyamide resin.
Hinge structure, beneficial effect of the present invention: the present invention is first by self-assembly method obtained polyaniline microsphere with hollow structure in poly-(2-acrylamide-2-methylpro panesulfonic acid) aqueous solution, again by doping method at polyaniline microsphere area load rare-earth cerium ion, obtain compound with regular structure, hollow polyaniline microspheres that pattern rule, area load that electric conductivity is high have rare-earth cerium ion.The area load that preparation method of the present invention obtains has hollow polyaniline microspheres compound with regular structure, the pattern rule of rare-earth cerium ion, for regular spherical, and the comparatively large (9.68m of specific surface area
2/ g), as can be seen from Figure 1 hollow microsphere external diameter is about 380nm, and hollow structure is intact, wall thickness is about 67nm; Effectively rare-earth cerium ion is carried on the ball wall surface of hollow polyaniline microspheres by the inventive method, area load has the specific conductivity of the hollow polyaniline microspheres of rare-earth cerium ion to reach 47.46S/cm, corrosion protection coating additive is it can be used as to prepare iron and steel corrosion-resistant coating, the corrosion potential of Electrochemical results display coating significantly improves, preservative effect is better, immersion measured result also display surface load has the polyaniline microsphere of rare-earth cerium ion to have good preservative effect, is a kind of well protective system additive.In addition, preparing area load has the method for the hollow polyaniline microspheres of rare-earth cerium ion easy, efficient, easy to control, is applicable to suitability for industrialized production.
Accompanying drawing explanation
[Fig. 1] has the scanning electron microscope diagram of the hollow polyaniline microspheres of rare-earth cerium ion, energy spectrum analysis figure and transmission electron microscope figure: a to be scanning electron microscope (SEM) photograph under 20,000 multiplying powers for the embodiment of the present invention 1 obtains area load; B is the scanning electron microscope (SEM) photograph under 100,000 multiplying powers; C corresponds to the energy spectrum analysis in a in rectangular area; D is transmission electron microscope picture.
[Fig. 2] has the infrared spectrogram of the hollow polyaniline microspheres of rare-earth cerium ion and the obtained hollow polyaniline microspheres of comparative example 1 for area load that embodiment 1 is obtained.
[Fig. 3] has the x-ray photoelectron spectroscopy analysis chart of the hollow polyaniline microspheres of rare-earth cerium ion for area load that embodiment 1 is obtained.
The area load that [Fig. 4] obtains for embodiment 1 has electroconductibility and the impedance chart of the hollow polyaniline microspheres of rare-earth cerium ion: a is conductivity map; B is impedance chart.
The area load that [Fig. 5] obtains for embodiment 1 has the hollow polyaniline microspheres of rare-earth cerium ion and hollow polyaniline microspheres to be mixed with the polarization curve of epoxy coat in iron-based material.
[Fig. 6] has the hollow polyaniline microspheres of rare-earth cerium ion and the obtained hollow polyaniline microspheres of comparative example 1 to be mixed with the optical picture of the anticorrosive test (720h) of epoxy coat in iron-based material for area load that embodiment 1 is obtained: a is PANI; B is PANI/Ce
3+.
Embodiment
Following specific embodiment is intended to further illustrate content of the present invention, and unrestricted the scope of protection of the invention.Embodiment 1
Get 6.32g dehydrated alcohol, the aqueous solution that 72.00g water, 2.08g contain poly-(2-acrylamide-2-methylpro panesulfonic acid) (being called for short PAMPS, massfraction 20%) joins in 250mL beaker, stir.Add 1.86g aniline subsequently in above-mentioned mixed solution, after ultrasonic 10min, the above-mentioned mixture system containing aniline is warming up to 80 DEG C, and magnetic agitation 10min at this temperature.Be 80 DEG C by temperature, the aqueous solution of the 40mL containing 4.56g ammonium persulphate adds in the above-mentioned mixed solution containing aniline fast, under agitation constant temperature 80 DEG C reaction 60s.Be in the ice-water bath of 0-5 DEG C, continue reaction 12h subsequently by reaction system transposition temperature.Use acetone breakdown of emulsion, washing, suction filtration, obtain hollow polyaniline microspheres.Joined by the hollow polyaniline microspheres obtained in the 50mL aqueous solution containing 0.36g cerous nitrate (III), room temperature lower magnetic force stirs 12h, and suction filtration, washing, drying obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.Carry out specific surface area test, specific surface area is 9.68m
2/ g.
By regulating the concentration of cerous nitrate (III), the hollow polyaniline microspheres of different cerium ion content can be obtained respectively.
There are by area load obtained above the hollow polyaniline microspheres 1.1g of rare-earth cerium ion, epoxy resin E-5115.0g, dimethylbenzene 4.5g, propyl carbinol 1.9g and a small amount of flow agent (BYK-306) to grind 3 times in conoidal mill, then are coated on steel surface (area 1.0 × 1.0cm after stirring with polyamide resin 6516.0g
2), smearing thickness controls at 40 ± 5 μm for electro-chemical test.Be 15.0 × 7.0cm by size in addition
2iron plate also apply coating, coating thickness controls at 200 ± 10 μm, and two mutually perpendicular length are 8.0cm on central zone is drawn, and width is that the straight line of 0.5cm is soaked in 3.5% sodium chloride brine and carries out erosion resistance experiment.
The area load of the electron scanning micrograph display preparation of Fig. 1 has the hollow polyaniline microspheres external diameter of rare-earth cerium ion to be about 380nm, the area load that transmission electron microscope figure shows preparation has the hollow polyaniline microspheres of rare-earth cerium ion to present hollow structure, and wall thickness is about about 67nm, ball internal diameter is about about 244nm.
Fig. 2 is the infrared spectrogram that area load has the hollow polyaniline microspheres of rare-earth cerium ion.1562cm
-1and 1490nm
-1be respectively quinone ring and the phenyl ring characteristic peak of polyaniline, confirm the existence of polyaniline.1645cm
-1for PAMPS characteristic peak.1142cm
-1for C-N telescope features peak, after rare earth doped cerium ion, this characteristic peak broadens, at 1105cm
-1place also occurs that peak position illustrates that cerium ion and electron rich N there occurs synergy.
Fig. 3 is the x-ray photoelectron spectroscopy figure that area load has the hollow polyaniline microspheres of rare-earth cerium ion, and wherein the appearance of cerium ion peak position also demonstrate that hollow polyaniline microspheres successfully adulterates load cerium ion.
The specific conductivity of the microballoon that Fig. 4 is prepared position and impedance data, the percentage composition that result demonstrates along with cerium ion increases, area load has the specific conductivity of the hollow polyaniline microspheres of rare-earth cerium ion to be increased to 46.76S/cm from 8.95S/cm always, and the charge-transfer resistance (arc radius) that impedance spectrum also shows microballoon also reduces gradually.
Table 1 is the energy spectrum analysis data of Fig. 1 (c)
| Element | wt％ | wt％Sigma |
| C | 72.05 | 0.61 |
| N | 13.40 | 0.68 |
| O | 10.56 | 0.24 |
| S | 3.12 | 0.05 |
| Ce | 0.88 | 0.05 |
| Total amount: | 100.00 |
Table 2 has the hollow polyaniline microspheres of rare-earth cerium ion to be mixed with epoxy coat preservative effect data in iron-based material for area load
Embodiment 2
Get 6.32g dehydrated alcohol, the aqueous solution that 72.00g water, 2.08g contain poly-(2-acrylamide-2-methylpro panesulfonic acid) (being called for short PAMPS, massfraction 40%) joins in 250mL beaker, stir.Add 1.86g aniline subsequently in above-mentioned mixed solution, after ultrasonic 10min, the above-mentioned mixture system containing aniline is warming up to 65 DEG C, and magnetic agitation 10min at this temperature.Be 65 DEG C by temperature, the aqueous solution of the 40mL containing 4.56g ammonium persulphate adds in the above-mentioned mixed solution containing aniline fast, under agitation constant temperature 65 DEG C reaction 80s.Be in the ice-water bath of 0-5 DEG C, continue reaction 6h subsequently by reaction system transposition temperature.Use acetone breakdown of emulsion, washing, suction filtration, obtain hollow polyaniline microspheres.Joined by the hollow polyaniline microspheres obtained in the 50mL aqueous solution containing 0.18g cerous nitrate (III), room temperature lower magnetic force stirs 8h, and suction filtration, washing, drying obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.Carry out specific surface area test, specific surface area 9.55m
2/ g.
There are by area load obtained above the hollow polyaniline microspheres 1.1g of rare-earth cerium ion, epoxy resin E-5115.0g, dimethylbenzene 4.5g, propyl carbinol 1.9g and a small amount of flow agent (BYK-306) to grind 3 times in conoidal mill, then are coated on steel surface (area 1.0 × 1.0cm after stirring with polyamide resin 6516.0g
2), smearing thickness controls at 40 ± 5 μm for electro-chemical test.Be 15.0 × 7.0cm by size in addition
2iron plate also apply coating, coating thickness controls at 200 ± 10 μm, and two mutually perpendicular length are 8.0cm on central zone is drawn, and width is that the straight line of 0.5cm is soaked in 3.5% sodium chloride brine and carries out erosion resistance experiment.The area load of specific conductivity test result display preparation has the specific conductivity of the hollow polyaniline microspheres of rare-earth cerium ion to be 31.79S/cm, the Electrochemical results display corrosion potential of the corrosion protection coating prepared with this filler is-0.383V, and corrosion electric current density is 1.367 × 10
-4μ A/cm
2, the coating of preparation has good preservative effect.
Comparative example 1
PANI hollow microsphere corrosion protection coating
Get 6.32g alcohol, 72.00g water, 2.08g contain poly-2-acrylamide-2-methylpro panesulfonic acid (being called for short PAMPS, massfraction 20%) the aqueous solution joins in 250mL beaker, stir.Add 1.86g aniline subsequently in above-mentioned mixed solution, after ultrasonic 10min, the above-mentioned mixture system containing aniline is warming up to 80 DEG C, and magnetic agitation 10min at this temperature.Be 80 DEG C by temperature, the aqueous solution of the 40mL containing 4.56g ammonium persulphate adds in the above-mentioned mixed solution containing aniline fast, under agitation constant temperature 80 DEG C reaction 60s.Be in the ice-water bath of 0-5 DEG C, continue reaction 12h subsequently by reaction system transposition temperature.Use acetone breakdown of emulsion, washing, suction filtration, obtain hollow polyaniline microspheres.Hollow polyaniline microspheres 1.1g obtained above, epoxy resin E-5115.0g, dimethylbenzene 4.5g, propyl carbinol 1.9g and a small amount of flow agent (BYK-306) are ground 3 times in conoidal mill, then is coated on steel surface (area 1.0 × 1.0cm after stirring with polyamide resin 6516.0g
2), coating thickness controls at 40 ± 5 μm for electro-chemical test.Be 15.0 × 7.0cm by size in addition
2iron plate also apply coating, coating thickness controls at 200 ± 10 μm, and two mutually perpendicular length are 8.0cm on central zone is drawn, and width is that the straight line of 0.5cm is soaked in 3.5% sodium chloride brine and carries out erosion resistance experiment.
The specific conductivity that detected result demonstrates hollow polyaniline microspheres is 8.95S/cm, and the charge-transfer resistance (arc radius) that impedance spectrum also shows hollow polyaniline microspheres is also than microballoon large being loaded with rare-earth cerium ion.The corrosion potential of Electrochemical results display polyaniline coating is-0.522V.
Claims (7)
1. an area load has the preparation method of the hollow polyaniline microspheres of rare-earth cerium ion, it is characterized in that, by poly-(2-acrylamide-2-methylpro panesulfonic acid), aniline, ammonium persulfate solution is added fast in the mixing solutions of second alcohol and water composition, first react at 50 ~ 80 DEG C of temperature, react further at 0 ~ 5 DEG C of temperature again, after having reacted, obtain hollow polyaniline microspheres, gained hollow polyaniline microspheres be placed in cerous nitrate (III) solution stir at 25 ~ 50 DEG C of temperature doping after, obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.
2. preparation method according to claim 1, it is characterized in that, described mixing solutions is made up of following mass percent component: poly-(2-acrylamide-2-methylpro panesulfonic acid) 0.5 ~ 4.9%, aniline 2.2 ~ 2.5%, ethanol 7.4 ~ 7.8%, water 84.8 ~ 89.9%.
3. preparation method according to claim 1, is characterized in that, described cerous nitrate (III) solution quality percentage concentration is 0.057 ~ 2.79%.
4. preparation method according to claim 1, is characterized in that, the time of reacting at 50 ~ 80 DEG C of temperature is 1 ~ 2min.
5. preparation method according to claim 1, is characterized in that, at 0 ~ 5 DEG C of temperature, the time of reaction is further 4 ~ 12h.
6. preparation method according to claim 1, is characterized in that, the time of stirring doping is 4 ~ 12h.
7. the preparation method according to any one of claim 1 ~ 6, it is characterized in that, (2-acrylamide-2-methylpro panesulfonic acid) will be gathered and aniline joins in ethanol/water mixed solvent, mix, obtain mixing solutions, the mass percent of mixing solutions consists of: poly-(2-acrylamide-2-methylpro panesulfonic acid) 0.5 ~ 4.9%, aniline 2.2 ~ 2.5%, ethanol 7.4 ~ 7.8%, water 84.8 ~ 89.9%; After gained mixed solution is warming up to 50 ~ 80 DEG C, add the ammonium persulfate aqueous solution that temperature is 50 ~ 80 DEG C fast, after holding temperature reaction 1 ~ 2min, adjust the temperature to 0 ~ 5 DEG C of reaction 4 ~ 12h further immediately; Breakdown of emulsion, washing, the hollow polyaniline microspheres obtained; Gained hollow polyaniline microspheres is placed in cerous nitrate (III) solution that mass percent concentration is 0.057 ~ 2.79%, doping 4 ~ 12h is stirred at 25 ~ 50 DEG C of temperature, suction filtration, washing, drying, obtain the hollow polyaniline microspheres that area load has rare-earth cerium ion.
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| CN113083175A (en) * | 2021-04-07 | 2021-07-09 | 信和新材料（苏州）有限公司 | Preparation method of corrosion inhibitor @ cerium dioxide microcapsule for anticorrosive paint |
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