CN100410295C - High temperature reflux oxidation process for preparing poly-o-phenylenediamine - Google Patents
High temperature reflux oxidation process for preparing poly-o-phenylenediamine Download PDFInfo
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- CN100410295C CN100410295C CNB2007100375267A CN200710037526A CN100410295C CN 100410295 C CN100410295 C CN 100410295C CN B2007100375267 A CNB2007100375267 A CN B2007100375267A CN 200710037526 A CN200710037526 A CN 200710037526A CN 100410295 C CN100410295 C CN 100410295C
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- phenylenediamine
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- high temperature
- oxidation process
- temperature reflux
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Abstract
The present invention relates to preparation of poly-o-phenylenediamine, and is especially high temperature reflux oxidation process for preparing poly-o-phenylenediamine. O-phenylenediamine monomer is first dissolved in glacial acetic acid, water solution of oxidant is then added into the monomer solution to produce reflux reaction, and the reacted product is treated to obtain poly-o-phenylenediamine. The present invention has glacial acetic acid as the reaction medium, high yield up to 80 % and dopped conductivity up to 3.0x10<-10> S/cm. The preparation process is simple, effective and high in yield.
Description
Technical field
The invention belongs to the preparation method field of poly-o-phenylenediamine.
Background technology
As a kind of important aromatic diamines base polymer, poly-o-phenylenediamine can provide more active free amino group and imido grpup, therefore poly-o-phenylenediamine has stronger electrochemical activity and multifunctionality than polyaniline, at aspects such as electrocatalysis, electrochromism, selective permeability and pH responses more superior performance is arranged.Poly-o-phenylenediamine can be used as the dispersion matrix of nano metal particles again as a kind of semi-conductivity organic materials simultaneously, utilizes the synergistic effect between metallic particles and conducting polymer, and increasing specific surface area promotes electrocatalysis characteristic.Poly-o-phenylenediamine is as a kind of novel electronic material, be expected to be applied to field (Yuan R such as electrocatalysis, electrode modification, transmitter, Zhang L Y, Li Q F, et al.A label-free amperometric immunosenor based onmulti-layer assembly of polymerized o-phenylenediamine and gold nanoparticles for determinationofJapanese B encephalitisvaccine[J] .Analytica Chimica Acta, 2005,531:1-5).
Electrochemical polymerization and chemical oxidising polymerisation often are used to synthetic aroma two amine polymers.In three isomer of phenylenediamine, Ursol D, mphenylenediamine all can issue biochemical oxypolymerization in the condition of gentleness, acquisition has polymkeric substance (the LiX G of higher yields, Huang M R, Duan W, et al.Novel multifunctional polymers from aromatic diamines byoxidative polymerizations[J] .Chemical Reviews, 2002,102:2925-3030).And the O-Phenylene Diamine polymerization activity is low, can't obtain the chemical oxidising polymerisation product generally speaking, only see report (the Komura T of its electropolymerization, Yamaguti T, Takahasi K.Impedance study of the charge transport at poly-o-phenylenediamine film electrodes[J] .Electrochimica Acta, 1996,41 (18): 2865-2870).Because the reacting environment of electropolymerization is near electrode surface, the output of polymkeric substance is subjected to the electrode area size-dependence, can't obtain a large amount of polymkeric substance.Therefore, develop a kind of new easy, economy, productive rate height, poly-o-phenylenediamine preparation method that suitability is strong is very important.
Summary of the invention
Purpose of the present invention solves a prior art difficult problem exactly, a kind of simple, economical and effective is provided, has the preparation method of the poly-o-phenylenediamine of good yield.
For reaching above-mentioned purpose, the concrete technical scheme that the present invention takes is as follows:
The high temperature reflux oxidation process for preparing of poly-o-phenylenediamine the steps include: the O-Phenylene Diamine monomer is dissolved in the glacial acetic acid, and the aqueous solution with oxygenant joins in the above-mentioned monomer solution then, back flow reaction, and the aftertreatment that reacts completely can obtain poly-o-phenylenediamine.
Spendable suitable oxygenant comprises ammonium persulphate ((NH among the present invention
4)
2S
2O
8), Potassium Persulphate (K
2S
2O
8) and iron trichloride (FeCl
3), be preferably ammonium persulphate.The consumption of oxygenant has very big influence to polymerization yield rate, and the monomeric mole of oxygenant and O-Phenylene Diamine proportion optimization is 1: 1 to 3: 1 among the present invention.
Because the O-Phenylene Diamine polymerization activity is low, polymerization at room temperature can only obtain the oligopolymer of O-Phenylene Diamine, therefore in the present invention, reacts in the ebullient glacial acetic acid, can provide to be higher than 100 ℃ temperature of reaction.Reaction times generally is controlled at 48～72h.
Adopt known method that polymerisate is handled among the present invention, removing monomer residual in the reaction mixture and oxygenant, and the oligopolymer that generates of reaction.Treatment step comprises natural subsidence, filtration, deionized water wash and drying.
Beneficial effect of the present invention: it is reaction medium that the present invention adopts glacial acetic acid, by the high temperature reflux oxidation synthesis method, has prepared the O-Phenylene Diamine polymkeric substance, has higher productive rate, reaches as high as about 80%, and the specific conductivity during doping reaches 3.0 * 10
-10S/cm.This method is simple, economical and effective, have good yield and general applicability.The present invention provides cost-effective new way for the preparation of poly-o-phenylenediamine, and the functional study for the exploitation poly-o-phenylenediamine provides basic substance simultaneously.
Description of drawings
Fig. 1 is the infrared spectrogram of high temperature reflux oxidation synthesis method synthetic poly-o-phenylenediamine under the different oxygen digital ratio.This collection of illustrative plates is at 3100～3600cm
-1Broad absorption band has appearred in the place, and this absorption band is a N-H stretching vibration characteristic absorbance, and the existence of free amino group and imido grpup in the polymkeric substance is described.The 1260cm that causes by the C-N stretching vibration in the polymkeric substance
-1The appearance of place's absorption peak illustrates-existence of C-NH-C-structure, and the generation of polymer P oPD has been described.
Fig. 2 is the wide-angle x-ray diffracting spectrum (oxygen digital ratio is 1/1, the doping attitude) of poly-o-phenylenediamine.This collection of illustrative plates has more wide in range disperse diffraction peak, and further illustrating the present invention, to have obtained the polymkeric substance and the polymerization degree of O-Phenylene Diamine really higher.
Embodiment
Embodiment 1:
Accurately take by weighing 6.48g (0.06mol) O-Phenylene Diamine monomer and add in the Glacial acetic acid, place 40 ℃ water-bath, stir and impel its dissolving.Took by weighing 13.68g (0.06mol) ammonium persulphate than 1: 1 by the oxygenant monomer, be transferred in the 100mL beaker and add and make it abundant dissolving in the 6mL deionized water.Oxidizing agent solution is added in the monomeric glacial acetic acid solution of O-Phenylene Diamine, continued back flow reaction 72 hours.Reaction finishes, filtration drying obtain the mixing black powder shape poly-o-phenylenediamine of attitude, and its infrared spectra is seen shown in Figure 1, its wide-angle x-ray diffracting spectrum is seen shown in Figure 2.
Output by the prepared O-Phenylene Diamine polymkeric substance of present embodiment is 2.59g, and productive rate is 40.0%.The specific conductivity of the polymer powder that records with pressed disc method is 1.8 * 10
-10S/cm.
Embodiment 2:
Accurately take by weighing 6.48g (0.06mol) O-Phenylene Diamine monomer and add in the Glacial acetic acid, place 40 ℃ water-bath, stir and impel its dissolving.Took by weighing 27.36g (0.12mol) ammonium persulphate than 2: 1 by the oxygenant monomer, be transferred in the 100ml beaker and add and make it abundant dissolving in the 6ml deionized water.Oxidizing agent solution is added in the monomeric glacial acetic acid solution of O-Phenylene Diamine, continued back flow reaction 72 hours.Reaction finishes, filtration drying obtain the mixing black powder shape poly-o-phenylenediamine of attitude, and its infrared spectra is seen shown in Figure 1.
Output by the prepared O-Phenylene Diamine polymkeric substance of present embodiment is 5.15g, and productive rate is 79.4%.The specific conductivity of the polymer powder that records with pressed disc method is 3.0 * 10
-10S/cm.
Embodiment 3:
Accurately take by weighing 6.48g (0.06mol) O-Phenylene Diamine monomer and add in the Glacial acetic acid, place 40 ℃ water-bath, stir and impel its dissolving.Took by weighing 41.04g (0.18mol) ammonium persulphate than 3: 1 by the oxygenant monomer, be transferred in the 100ml beaker and add and make it abundant dissolving in the 6ml deionized water.Oxidizing agent solution is added in the monomeric glacial acetic acid solution of O-Phenylene Diamine, continued back flow reaction 72 hours.Reaction finishes, filtration drying obtain the mixing black powder shape poly-o-phenylenediamine of attitude, and its infrared spectra is seen shown in Figure 1.
Output by the prepared O-Phenylene Diamine polymkeric substance of present embodiment is 4.61g, and productive rate is 71.2%, and specific conductivity is less than 1 * 10
-12S/cm.
Embodiment 4:
Get the product among the embodiment 1, it is soaked, stirs 24h in ammoniacal liquor or sodium hydroxide solution, it is 1: 1 that filtration drying obtains oxygen digital ratio, the poly-o-phenylenediamine of the attitude of going to mix, and its specific conductivity is less than 1 * 10
-12S/cm.
Embodiment 5:
Get the product among the embodiment 2, it is soaked, stirs 24h in ammoniacal liquor or sodium hydroxide solution, it is 2: 1 that filtration drying obtains oxygen digital ratio, the poly-o-phenylenediamine particle of the attitude of going to mix, and its specific conductivity is less than 1 * 10
-12S/em.
Embodiment 6:
Get the product among the embodiment 3, it is soaked, stirs 24h in ammoniacal liquor or sodium hydroxide solution, it is 3: 1 that filtration drying obtains oxygen digital ratio, the poly-o-phenylenediamine particle of the attitude of going to mix, and its specific conductivity is less than 1 * 10
-12S/cm.
Claims (5)
1. the high temperature reflux oxidation process for preparing of poly-o-phenylenediamine the steps include: the O-Phenylene Diamine monomer is dissolved in the glacial acetic acid, and the aqueous solution with oxygenant joins in the above-mentioned monomer solution then, back flow reaction, and the aftertreatment that reacts completely can obtain poly-o-phenylenediamine.
2. the high temperature reflux oxidation process for preparing of poly-o-phenylenediamine as claimed in claim 1, it is characterized in that: oxygenant is ammonium persulphate, Potassium Persulphate or iron trichloride.
3. the high temperature reflux oxidation process for preparing of poly-o-phenylenediamine as claimed in claim 2, it is characterized in that: oxygenant is an ammonium persulphate.
4. the high temperature reflux oxidation process for preparing of poly-o-phenylenediamine as claimed in claim 1 is characterized in that: the monomeric mole of oxygenant and O-Phenylene Diamine proportioning is 1: 1 to 3: 1.
5. the high temperature reflux oxidation process for preparing of poly-o-phenylenediamine as claimed in claim 1, it is characterized in that: the reaction times is 48～72h.
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|---|---|---|---|---|
| CN102683041B (en) * | 2012-06-01 | 2014-05-28 | 扬州大学 | Electrochemical synthesis method of poly-o-phenylenediamine non-membrane material and application of poly-o-phenylenediamine non-membrane material in super capacitor |
| CN103694471B (en) * | 2013-12-25 | 2015-07-15 | 哈尔滨工业大学 | Method for preparing poly(o-phenylenediamine) nanomicelle by utilizing aqueous phase method |
| CN103694473B (en) * | 2013-12-25 | 2015-12-02 | 哈尔滨工业大学 | Aqueous phase prepares the method for poly-o-phenylenediamine nano belt |
| CN106977919B (en) * | 2016-01-19 | 2019-02-01 | 同济大学 | A kind of poly- p-phenylenediamine powder of high Seebeck coefficient and its preparation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050277757A1 (en) * | 2004-06-15 | 2005-12-15 | Erkang Wang | Method for preparation of poly(o-phenylenediamine) Nano-belt |
| CN1840235A (en) * | 2005-03-30 | 2006-10-04 | 同济大学 | Use of Pb ion absorbent of polyphenylene diamine |
| CN1854169A (en) * | 2005-04-19 | 2006-11-01 | 中国科学院金属研究所 | Production of polyaniline micro/nanometer fibre |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050277757A1 (en) * | 2004-06-15 | 2005-12-15 | Erkang Wang | Method for preparation of poly(o-phenylenediamine) Nano-belt |
| CN1840235A (en) * | 2005-03-30 | 2006-10-04 | 同济大学 | Use of Pb ion absorbent of polyphenylene diamine |
| CN1854169A (en) * | 2005-04-19 | 2006-11-01 | 中国科学院金属研究所 | Production of polyaniline micro/nanometer fibre |
Non-Patent Citations (4)
| Title |
|---|
| 沙林酸印迹聚邻苯二胺纳米膜制备及结构表征. 左言军.物理化学学报，第19卷第6期. 2003 |
| 沙林酸印迹聚邻苯二胺纳米膜制备及结构表征. 左言军.物理化学学报，第19卷第6期. 2003 * |
| 芳香族二胺聚合物修饰电极对痕量重金属离子的络合与探测. 黄美荣.分析测试学报，第24卷第2期. 2005 |
| 芳香族二胺聚合物修饰电极对痕量重金属离子的络合与探测. 黄美荣.分析测试学报，第24卷第2期. 2005 * |
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