CN100398582C - Process for preparing polyanilinechloride - Google Patents
Process for preparing polyanilinechloride Download PDFInfo
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- CN100398582C CN100398582C CNB021215723A CN02121572A CN100398582C CN 100398582 C CN100398582 C CN 100398582C CN B021215723 A CNB021215723 A CN B021215723A CN 02121572 A CN02121572 A CN 02121572A CN 100398582 C CN100398582 C CN 100398582C
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- polyaniline
- chloropolyaniline
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Abstract
The present invention relates to a preparation method for chloropolyaniline. The heating and the refluxing of polyaniline and sulfur monochloride are carried out in a polar aprotic solvent under the action of the catalysis of Lewis acid to prepare the chloropolyaniline. Every 6 carbon atoms of the chloropolyaniline contain 2 to 3 chlorine atoms, the yield rate of the chloropolyaniline reaches 93 to 97%, and the chloropolyaniline can be used as the precursor raw material of the anode material of a lithium secondary cell.
Description
Affiliated technical field
The present invention relates to a kind of preparation method of chloropolyaniline, the preparation method of especially many chloropolyanilines.
Background technology
Since people such as MacDiarmidAG in 1987 first since the chemosynthesis electrically conductive polyaniline, people's p-poly-phenyl amine and derivative thereof have carried out extensive and deep research, but to the polyaniline derivative report that contains electrophilic halogen functional group on the phenyl ring seldom.People such as Korea S Kang D P utilize 2-chloro aminobenzen and 2-fluorobenzene amine monomers to prepare poly-2-chloro aminobenzen and poly-2-fluoro aniline through radical polymerization under the oxygenizement of chromic acid, do not introduce reaction yield, but analyzed the influence of monomer structure polyreaction.The author thinks that the substituted radical electronegativity that contains on the monomer phenyl ring is big more, and then the oxidation activity of anils is low more, thus polyreaction difficult more (seeing Synthetic Metals 1997,84,95～96).U.S. KwonAH and its colleague adopt the ammonium persulphate oxygenant make monomer 2-fluoro aniline and 3-fluoro aniline respectively polyreaction obtained poly-2-fluoro aniline and poly-3-fluoro aniline, reaction yield is 3～7% (to see Synthetic Metals 1989,29, E343-E348).Above document all is to utilize the halogeno-benzene amine monomers through the directly synthetic poly-halo aniline of radical polymerization, and chemical structure is more clearly, but productive rate is not good enough.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing chloropolyaniline, that is: under strong lewis acid catalysis halogenating reaction takes place by polyaniline and sulfur monochloride in polar aprotic solvent, 2～3 chlorine atoms of per 6 carbon atom bondings of chloropolyaniline of preparation, productive rate reaches 93%.
The preparation method of the chloropolyaniline that the present invention relates to is a polyaniline: sulfur monochloride: the mol ratio of lewis acid catalyst is 1: 1～10: 0.5～8, every 1mmol polyaniline uses polar aprotic solvent 2～6ml, temperature of reaction is 80～180 ℃, and the reaction times is 6～24h.
The polyaniline that the present invention relates to is a partial oxidation attitude polyaniline, and its chemical structural formula is:
0.25≤y≤1 wherein, y=1 is for going back the ortho states polyaniline entirely, and 0.25≤y＜1 is a partial oxidation attitude polyaniline.
The strong lewis acid catalyzer that the present invention relates to is Zinc Chloride Anhydrous (ZnCl
2), aluminum trichloride (anhydrous) (AlCl
3), FERRIC CHLORIDE ANHYDROUS (FeCl
3), anhydrous antimony pentachloride (SbCl
5) and anhydrous stannic chloride (SnCl
4) etc.
The polar aprotic solvent that the present invention relates to is acetonitrile, dimethyl sulfoxide (DMSO) (DMSO), N, dinethylformamide (DMF), N-methyl 2-Pyrrolidone (NMP) etc.
Prepare many chloropolyanilines by polyaniline and sulfur monochloride under the Louis acid catalysis effect, chemical equation is:
0.25≤y≤1 wherein.
Many chloropolyanilines can be as the precursor raw material of anode material for lithium secondary battery, and the theoretical specific capacity of the polythio polyaniline that the sulfuration back obtains is higher than 500mAh/g.
Description of drawings
The scanning electron microscope spectrogram of chloropolyaniline.
Embodiment
Embodiment 1
Successively add 3.0g (33mmol) polyaniline, 11.0g (82mmol) aluminum trichloride (anhydrous) and 13ml (165mmol) sulfur monochloride in three mouthfuls of round-bottomed flasks of 250ml, then drip the 100ml anhydrous acetonitrile, slowly heating then continues stirring and refluxing reaction 10h.After reaction finishes, filter, with dithiocarbonic anhydride Ti Shi extraction 10h, soak after (PH=8～9) spend the night 1mol/L hydrochloric acid soln washing 30ml * 20 time, 0.1mol/L ammoniacal liquor, 0.1mol/L ammonia scrubbing 20ml * 15 times, last 60 ℃ of vacuum-drying 24h, obtain 6.0g black powdery solid chloropolyaniline, according to generating three chloro polyaniline meters, yield is 93%.Results of elemental analyses (wt%) is: C 37.64, and N 7.66, and H 1.10, and S 3.18, and Cl 50.32.FT-IR(KBr，cm
-1)：3375，3057，1671，1582，1474，1359，1223，1127，1080，1036，866，819，574。The electronic scanning Electronic Speculum spectrogram of chloropolyaniline is seen accompanying drawing.
Embodiment 2
Successively add 4.50g (49.5mmol) polyaniline, 36.5g (272mmol) aluminum trichloride (anhydrous) and 24ml (165mmol) sulfur monochloride in three mouthfuls of round-bottomed flasks of 250ml, then drip 150mlDMF, slowly heating then continues stirring and refluxing reaction 12h.After reaction finishes, filter, ether washing 100ml * 5 time, dithiocarbonic anhydride washing 50ml * 8 time, go to distilled water wash 50ml * 10 time, soak after (PH=8～9) spend the night with 250ml 1mol/L ammoniacal liquor then, with 0.1mol/L ammonia scrubbing 50ml * 10 times, last 80 ℃ of vacuum-drying 48h obtain 10.0g black powdery solid chloropolyaniline.Results of elemental analyses (wt%) is: C 33.83, N6.86, and H 0.92, and S 5.20, and Cl 48.36.FT-IR(KBr，cm
-1)：3380，1586，1477，1230，1128，1079，1037，945，825，707，481。
Embodiment 3
3.5g polyaniline, 3.8ml phenylhydrazine, 100ml anhydrous diethyl ether are joined in the 150ml round-bottomed flask, at room temperature react 8h.After reaction finishes, filter, ether washing 30ml * 6,80 ℃ of vacuum-drying 6h obtain 3.5g black powdery solid and go back the ortho states polyaniline entirely then.
In the 100ml single necked round bottom flask, add 0.5g successively and go back ortho states polyaniline, 3.3g aluminum trichloride (anhydrous) and 2.2ml sulfur monochloride entirely, drip the 30ml anhydrous acetonitrile again, continue stirring heating back flow reaction 10h then.Reaction finishes, and filters, with dithiocarbonic anhydride Ti Shi extraction 10h, with 1mol/L salt acid elution 30ml * 20 times, 150ml 0.1mol/L ammoniacal liquor soaks 24h, uses 0.1mol/L ammonia scrubbing 30ml * 15 times again, last 60 ℃ of vacuum-drying 24h obtain 1.1g black powdery solid chloropolyaniline.Results of elemental analyses (wt%) is: C 35.62, and N 7.05, and H 0.74, and S 6.57, and Cl 48.53.
Claims (3)
1. the preparation method of a chloropolyaniline is characterized in that polyaniline and sulfur monochloride through strong lewis acid catalysis prepared in reaction in polar aprotic solvent, and the chemical structural formula of this polyaniline is:
Reactant batching mol ratio is a polyaniline: sulfur monochloride: Lewis acid=1: 1～10: 0.5～8; Every 1mmol polyaniline uses 2～6ml polar aprotic solvent; Temperature of reaction is 80～180 ℃; Reaction times is 6～24h.
2. preparation method according to claim 1 is characterized in that Lewis acid is Zinc Chloride Anhydrous, aluminum trichloride (anhydrous), FERRIC CHLORIDE ANHYDROUS, anhydrous antimony pentachloride and anhydrous stannic chloride.
3. preparation method according to claim 1 is characterized in that polar aprotic solvent is acetonitrile, dimethyl sulfoxide (DMSO), N, dinethylformamide, N-N-methyl-2-2-pyrrolidone N-.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021215723A CN100398582C (en) | 2002-06-26 | 2002-06-26 | Process for preparing polyanilinechloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021215723A CN100398582C (en) | 2002-06-26 | 2002-06-26 | Process for preparing polyanilinechloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1465610A CN1465610A (en) | 2004-01-07 |
| CN100398582C true CN100398582C (en) | 2008-07-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021215723A Expired - Fee Related CN100398582C (en) | 2002-06-26 | 2002-06-26 | Process for preparing polyanilinechloride |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995621A (en) * | 2017-04-26 | 2017-08-01 | 天津大学 | Ring substituting modification anticorrosive polyaniline, antifouling difunctional composite coating and preparation method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059914A (en) * | 1986-03-24 | 1992-04-01 | 加利福尼亚大学董事会 | The preparation method of method of preparation of self-doped polymers |
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2002
- 2002-06-26 CN CNB021215723A patent/CN100398582C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1059914A (en) * | 1986-03-24 | 1992-04-01 | 加利福尼亚大学董事会 | The preparation method of method of preparation of self-doped polymers |
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| CN1465610A (en) | 2004-01-07 |
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Granted publication date: 20080702 Termination date: 20100626 |