CN101165092B - Method for preparing electric polypyrrole nano hollow sphere - Google Patents
Method for preparing electric polypyrrole nano hollow sphere Download PDFInfo
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- CN101165092B CN101165092B CN200610032410XA CN200610032410A CN101165092B CN 101165092 B CN101165092 B CN 101165092B CN 200610032410X A CN200610032410X A CN 200610032410XA CN 200610032410 A CN200610032410 A CN 200610032410A CN 101165092 B CN101165092 B CN 101165092B
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Abstract
The process of preparing composite particle of hollow nanometer conductive polypyrrole-silica ball includes the following successive steps: adding pyrrole monomer and nanometer silica ball into deionized water and dispersing ultrasonically; and introducing initiator to react at 100-180 deg.c to obtain the composite particle. Compared with available technology, the process of the present invention has the advantages of less intermediate steps, low cost, capacity of obtaining product with high size homogeneity and controllability, and other advantages.
Description
Technical field
The present invention relates to a kind of preparation method of high molecular nanometer hollow ball, particularly a kind of preparation method of compound nano-hollow sphere of electric polypyrrole.
Background technology
Polypyrrole has electroconductibility, chemistry and hot stability, can be used as the material that a kind of medium absorbs and discharge characteristic such as some biomacromolecule material, and the potential using value in biomedical sector is being studied; Can be widely used in industries such as coating, paint, papermaking, leather, makeup as white plastic pigment, uvioresistant additive and the feel properties-correcting agent etc. of paint and water-borne coatings.Simultaneously polypyrrole is nontoxic, no pyrogeneous substance, does not cause haemolysis and allergy, does not also have a material of mutagenesis and hormesis, has good biological safety, so its another important use is as microcapsule, encapsulation function compound in it is hollow is made the macromolecular material with slow-release function.
The present existing method for preparing the empty ball of polypyrrole has two kinds: the one, and gas/liquid phase method, but its empty ball of preparing is not of uniform size, and complicated operation, be difficult to drop into actual production; The 2nd, template, this method have multiple realization approach, as utilize polystyrene modified ball and the empty ball of pyrroles's prepared in reaction polypyrrole; Utilization is adsorbed the pyrroles coat polyvinylpyrrolidone on silicon dioxide microsphere after again, prepares the microballoon of polypyrrole and polyvinylpyrrolidone coexistence then with the method for chemical polymerization; Doing nuclear with gold finishes and removes karyomorphism again after the coating of polypyrrole and become the empty ball of polypyrrole; Use Fe
3Cl is as initiator, and synthetic in the solution that has chitosan to exist is the polypyrrole nano composite sphere of nuclear with AgCl, removes AgCl nuclear again; All there is complex disposal process in above method, and final product purity is not enough and productive expense is too high, is difficult for shortcomings such as industrialization.
Summary of the invention
The objective of the invention is to the problem at the prior art existence, a kind of preparation method of polypyrrole hollow ball is provided, the polypyrrole hollow ball of its production has good biological safety, stronger specific conductivity, and density is low, and specific surface area is big.
The preparation method of electric polypyrrole nano hollow sphere adds pyrrole monomer, silica nanosphere successively in deionized water, adopt ultra-sonic dispersion that pyrrole monomer and silica nanosphere are uniformly dispersed in water; Add initiator after being uniformly dispersed, reacted 4～8 hours down, obtain the composite particles that the black insolubles is electric polypyrrole and silica nanosphere at 100～180 ℃.
The add-on of described pyrrole monomer is 0.6-30 milliliter pyrrole monomer/L water.
Described silica nanosphere add-on is a 1-40g/L water, and its particle diameter is the 50-300 nanometer.
Described initiator comprises: ammonium persulfate, Potassium Persulphate, Sodium Persulfate, FERRIC CHLORIDE ANHYDROUS, hydrogen peroxide or nitric acid; The mol ratio of initiator and pyrrole monomer is 1: 0.1-10.
The ultrasonic power of described ultra-sonic dispersion is 600-2400W, and ultrasonic frequency is 19-80KHz.
In order to obtain the composite particles of higher degree, can filter, wash with ethanol, distilled water composite particles, to remove various impurity.
The electric polypyrrole nano hollow sphere of the present invention preparation can be in ethanol ultra-sonic dispersion, adopt the structure and the pattern of means observation nano-hollow balls such as scanning electron microscope or transmission electron microscope then.The diameter of the electric polypyrrole nano hollow sphere that synthesizes is in the 100-500 nanometer, wall thickness 50-100 nanometer.
Method of the present invention can be carried out scale operation, no scale restriction; Compare with the method that with the polystyrene spheres is nuclear, the present invention need not handle silica nanosphere, can carry out in-situ oxidation and form the polypyrrole shell directly its surface adsorption pyrroles, has reduced intermediate steps, provides cost savings; Silica spheres adsorbs the pyrroles afterwards again, the preparation method of chemical polymerization has exempted the silica sphere treating processes then with handling with polyvinylpyrrolidone, reduced middle process equally, save cost, and final product do not contain other high molecular polymer, and its later stage processing and utilization is not had influence; The advantage of comparing with preparation method with Jin Weihe is to be to use cheap core particle, has avoided waste and recovery cost on post-processed; And than the preparation method who with AgCl is nuclear, the nano-hollow ball size homogeneous of the inventive method preparation, size can be regulated and control.
Description of drawings
Fig. 1 is the stereoscan photograph of polypyrrole nano-hollow ball;
Fig. 2 is the transmission electron microscope photo of polypyrrole nano-hollow ball.
Embodiment
The preparation of embodiment 1, polypyrrole nano-hollow ball
Weighing 0.15g silica nanosphere adds in the 30ml deionized water, ultra-sonic dispersion 15 minutes, add the 0.1ml pyrrole monomer again, the capping system ultra-sonic dispersion 30-45 minute, fully is uniformly dispersed pyrrole monomer and silica nanosphere, reaction system is transferred to reactor, after adding ammonium persulfate aqueous solution (the 0.15g ammonium persulphate is dissolved in the 7.5ml deionized water), reacted 4 hours down at 180 ℃, filtration, washing obtain the compound nucleus shell particles; In the hydrofluoric acid with composite particles adding 37%, react after 12-24 hour, use in the sodium hydroxide solution and the unreacted hydrogen fluoric acid, the black insolubles is filtered, washes, absolute ethanol washing.Collect the black filter cake that washing finishes.
Synthetic polypyrrole nano-hollow ball as shown in Figure 1, the diameter homogeneous of the empty ball of nanometer is 450 nanometers.
The preparation of embodiment 2, polypyrrole nano-hollow ball
Weighing 1.5g silica nanosphere adds in the 30ml deionized water, ultra-sonic dispersion 15 minutes, add the 1ml pyrrole monomer again, the capping system ultra-sonic dispersion 30-45 minute, fully is uniformly dispersed pyrrole monomer and silica nanosphere, reaction system is transferred to reactor, after adding ammonium persulfate aqueous solution (the 0.15g ammonium persulphate is dissolved in the 7.5ml deionized water), reacted 8 hours down at 100 ℃, filtration, washing obtain the compound nucleus shell particles; In the hydrofluoric acid with composite particles adding 37%, react after 12-24 hour, use in the sodium hydroxide solution and the unreacted hydrogen fluoric acid, the black insolubles is filtered, washes, absolute ethanol washing.Collect the black filter cake that washing finishes.
Synthetic polypyrrole nano-hollow ball as shown in Figure 2, the diameter homogeneous of the empty ball of nanometer is 480 nanometers, shell polypyrrole thickness increases to some extent.
Claims (1)
1. the preparation method of electric polypyrrole nano hollow sphere is characterized in that: add pyrrole monomer, silica nanosphere successively in deionized water, adopt ultra-sonic dispersion that pyrrole monomer and silica nanosphere are uniformly dispersed in water; Add initiator after being uniformly dispersed, reacted 4～8 hours down, obtain the composite particles of electric polypyrrole and silica nanosphere at 100～180 ℃;
The add-on of described pyrrole monomer is 0.6-30 milliliter pyrrole monomer/L water;
Described silica nanosphere add-on is a 1-40g/L water, and its particle diameter is the 50-300 nanometer;
Described initiator comprises: ammonium persulphate, Potassium Persulphate, Sodium Persulfate, FERRIC CHLORIDE ANHYDROUS, hydrogen peroxide or nitric acid; The mol ratio of initiator and pyrrole monomer is 1: 0.1-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN200610032410XA CN101165092B (en) | 2006-10-16 | 2006-10-16 | Method for preparing electric polypyrrole nano hollow sphere |
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| CN200610032410XA CN101165092B (en) | 2006-10-16 | 2006-10-16 | Method for preparing electric polypyrrole nano hollow sphere |
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| CN101165092A CN101165092A (en) | 2008-04-23 |
| CN101165092B true CN101165092B (en) | 2011-04-27 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391510B (en) * | 2011-07-13 | 2012-12-26 | 扬州大学 | Production method for synthesizing polypyrrole hollow spheres by self template process |
| CN103972482A (en) * | 2013-02-06 | 2014-08-06 | 苏州宝时得电动工具有限公司 | Preparation method for complex, positive electrode and battery both containing same |
| CN103259000A (en) * | 2013-04-25 | 2013-08-21 | 浙江师范大学 | Polypyrrole hollow microsphere/ sulfur composite material as well as preparation method and application thereof |
| CN105400362A (en) * | 2015-11-14 | 2016-03-16 | 合肥标兵凯基新型材料有限公司 | Epoxy resin coating with good flexibility and excellent adhesive force |
| CN105400380A (en) * | 2015-11-14 | 2016-03-16 | 合肥标兵凯基新型材料有限公司 | Modified epoxy resin coating |
| CN109550467B (en) * | 2018-11-29 | 2020-10-30 | 江南大学 | Conductive composite shell material hollow microsphere and preparation method thereof |
| CN110201715B (en) * | 2019-05-15 | 2022-06-14 | 上海大学 | Non-noble metal CO derived from iron-doped polymers2Reductive composite catalyst, preparation method and application thereof |
| CN111974322A (en) * | 2019-05-23 | 2020-11-24 | 天津工业大学 | Polypyrrole porous hollow nano-microsphere and preparation method and application thereof |
| CN117004449B (en) * | 2023-08-01 | 2024-06-14 | 东营科技职业学院 | Preparation method of additive, additive and application of additive in lubricating oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358775A (en) * | 2001-12-26 | 2002-07-17 | 河北工业大学 | Polypyrrole/silicon dioxide nano composite material and preparation process thereof |
| CN1515629A (en) * | 2003-01-10 | 2004-07-28 | 中国科学院成都有机化学研究所 | Nano high-molecular microsphere with conductivity and magnetism and its preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1358775A (en) * | 2001-12-26 | 2002-07-17 | 河北工业大学 | Polypyrrole/silicon dioxide nano composite material and preparation process thereof |
| CN1515629A (en) * | 2003-01-10 | 2004-07-28 | 中国科学院成都有机化学研究所 | Nano high-molecular microsphere with conductivity and magnetism and its preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 杨伏勇.以SiO2粒子为模板合成功能性核壳材料.中国优秀硕士学位论文全文数据库 2006年第09期.2006,(2006年第09期),第32、36、37、46页. |
| 杨伏勇.以SiO2粒子为模板合成功能性核壳材料.中国优秀硕士学位论文全文数据库 2006年第09期.2006,(2006年第09期),第32、36、37、46页. * |
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