CN1088454C - Synthetic method of electroactive large monomer - Google Patents
Synthetic method of electroactive large monomer Download PDFInfo
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- CN1088454C CN1088454C CN98108689A CN98108689A CN1088454C CN 1088454 C CN1088454 C CN 1088454C CN 98108689 A CN98108689 A CN 98108689A CN 98108689 A CN98108689 A CN 98108689A CN 1088454 C CN1088454 C CN 1088454C
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- electroactive
- reaction
- synthetic method
- aniline
- macromer
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Abstract
The present invention belongs to a technology for synthesizing the electroactive macromer, which uses polyfunctional compounds to protect the terminal amido of aniline dipolymer, trimer and tetramer, or uses the substituendum of diphenylamine to react with p-phenylenediamine at room temperature to obtain the electroactive macromer. The present invention has the characteristics of simple synthetic route and convenient operation, and the electroactive polymer which is prepared by the reaction of the electroactive macromer and the traditional monomer makes the technology widely applied to the fields of the anti-static material and the corrosion-resistant material.
Description
The invention belongs to the synthetic technology of electroactive large monomer.
That polyaniline has is easily synthetic, can stable existence in air, characteristics such as unique doping phenomenon, excellent electrochemical reversibility, in the past few decades, it has been carried out deep research both at home and abroad.Polyaniline has obtained some application at aspects such as battery, sensor, corrosion resistant materials.Because polyaniline is insoluble not molten, therefore, has limited it and has used widely.
In recent years, started the upsurge of research polyaniline oligomer abroad.People such as Wudl had synthesized end capped eight aggressiveness of benzene in 1985, it is reported that its electric conductivity and spectral quality are in close proximity to polyaniline.People such as MacDiarmid and Yan Wei have pushed ahead major step to the research work of polyaniline oligomer recently.It is that benzene one end is the tetramer, eight aggressiveness and 16 aggressiveness of amido that people such as MacDiarmid have synthesized an end, and the sensitivity of finding the sensor made with eight aggressiveness is than high several thousand times of polyaniline; People such as Yan Wei are raw material with Ursol D and aniline, having synthesized two ends all is amine-terminated polyaniline tripolymer, they are again from tripolymer, synthesized a series of polyaniline oligomer with definite polymerization degree, they have also synthesized a series of superpolymer with tripolymer, and its corrosion resistance studied, found that its corrosion resistance will be better than polyaniline far away.
The method of people's synthesized polyaniline oligopolymers such as Yan Wei be difficult to stop trimerical further oxidative coupling, thereby by product is a lot, and needs extremely low temperature of reaction, and not easy to operate, the tripolymer that obtains at room temperature can not stable existence.People such as MacDiarmid one end has the oligopolymer of amido at room temperature can not stable existence.
Our synthetic route because protected the end amido or do not contained the end amido, thereby has stoped its further reaction; so reduced by product, being reflected at room temperature can carry out, and condition as mild as a dove; easily operation, but and the compound that obtains stable existence at room temperature.
Our synthetic electroactive large monomer, have can with the further polymeric of traditional monomer functional group, can be used to the synthesis of electroactive polymkeric substance, this just can change the insoluble infusible weakness of polyaniline, inherit its excellent advantage such as electrochemical reversibility, thereby it is more widely used at aspects such as antistatic material, corrosion resistant materials.
The present invention adopts Ursol D and compound a and a ' under acidic conditions, synthetic big monomer b of oxidative coupling and b '.The following first kind of its reaction expression:
R:-CH
2CH
2-,-CH=CH-
N=1,2,3 m=3,5,7 second classes:
R:COOH, Br, OH, SO
3H, Cl characteristics of the present invention are:
1 aniline dimer, tripolymer, tetrameric end amido are had multi-functional compound protection by some; the substituent of pentanoic does not contain the end amido; thereby stoped its further oxidative coupling; reaction does not need extremely low temperature of reaction; can be-5～30 ℃ of adjustings; synthetic route is simple, and is easy to operate.And the synthetic compound have can with the functional group of traditional monomer polymerization.Can be used for the synthesis of electroactive polymkeric substance.
2 synthetic electroactive large monomers of the present invention, but stable existence at room temperature at room temperature can not stable existences thereby overcome people's synthetic oligopolymers such as Yan Wei and MacDiarmid, need the weakness of freezing preservation.
3 reactions will be carried out in acid system, and the concentration of the acid of system can be regulated between 5M～0.5M.
4 oxygenants can be selected (NH for use
4)
2S
2O
8Or FeCl
36H
2O, Ce (SO
4)
2, KMnO
4, KBrO
3, K
2Cr
2O
7, KIO
3, NaClO, H
2O
2, (NH wherein
4)
2S
2O
8Or FeCl
36H
2O is better.
Embodiment 1a:
In the there-necked flask that the product of stirring are housed, add 2.85g (0.01mol) a and 0.54g (0.005mol) Ursol D, add 15ml DMF then, the dissolving back adds 80ml refrigerative mixed solvent (30ml DMF, 25ml distilled water in advance, the 25ml concentrated hydrochloric acid), with 2.74g (NH
4)
2S
2O
8(0.012mol) be dissolved in the dilute hydrochloric acid of 50ml 1M, it added reaction system lentamente with dropping funnel.Temperature of reaction: room temperature; The dropping time: 1 hour.Dropwised afterreaction 1 hour, reaction liquid is poured in the 500ml distilled water, suction filtration, with distillation washing twice, each adding distil water 500ml, the product that obtains is transferred to alkalescence with ammoniacal liquor, reduced 0.5～1 hour with hydrazine hydrate or anhydrous hydrazine, transfer to pH with hydrochloric acid and equal 1～2, suction filtration, with 500ml distillation washing twice, the product that obtains is dried under vacuum then.Obtain powder 3.00g, productive rate 88%.
Embodiment 2
Reaction just changes the consumption of oxygenant with embodiment 1: be about to 2.28g (NH
4)
2S
2O
8(0.01mol) be dissolved in the dilute hydrochloric acid of 50ml 1M, it added reaction system lentamente with dropping funnel.Obtain powder 2.74g, productive rate 80%.
Embodiment 3
Reaction just changes temperature of reaction with embodiment 1.Temperature of reaction: 30 ℃.Obtain powder 2.50g, productive rate 74%.
Embodiment 4
Reaction just changes the concentration of acid with embodiment 1.Add 2.85g (0.01mol) a monomer and 0.54g (0.005mol) Ursol D in there-necked flask, add 15ml DMF then, the dissolving back adds 80ml refrigerative mixed solvent (30ml DMF, 20ml H in advance
2O, the 30ml concentrated hydrochloric acid).Obtain powder 2.30g, productive rate 68%.
Embodiment 5
Reaction just changes the kind of oxygenant with embodiment 1.With 3.24g FeCl
36H
2O is dissolved in the dilute hydrochloric acid of 50ml 1M, with dropping funnel it is added reaction system lentamente.To powder 2.03g, productive rate 60%.
Embodiment 6a ':
Reaction just changes the kind of a with embodiment 1.Add 2.04g (0.01mol) a ' monomer and 0.54g (0.005mol) Ursol D in there-necked flask, add 15ml DMF then, the dissolving back adds 80ml refrigerative mixed solvent (30ml DMF, 20ml H in advance
2O, the 30ml concentrated hydrochloric acid).Obtain powder 1.89g, productive rate 74%.Annotate: the cumulative volume of reaction system before the dropping oxidizing agent of the mole number of acid before the dropping oxidizing agent of the concentration of acid=not/not
Claims (5)
1 one kinds of polymeric synthetic methods of electroactive aniline is characterized in that in acid system, carrying out the synthetic first kind of electroactive large monomer under the condition of certain temperature and oxygenant existence:
R:-CH
2CH
2-,-CH=CH-
N=1,2,3 m=3,5,7 second classes:
R:COOH, Br, OH, SO
3H, Cl.
The polymeric synthetic method of 2 electroactive aniline as claimed in claim 1 is characterized in that temperature of reaction is-5～30 ℃.
The polymeric synthetic method of 3 electroactive aniline as claimed in claim 1, the concentration that it is characterized in that reaction acid is 0.5M～5M.
The polymeric synthetic method of 4 electroactive aniline as claimed in claim 1 is characterized in that oxygenant is (NH
4)
2S
2O
8Or FeCl
36H
2O, Ce (SO
4)
2, KMnO
4, KBrO
3, K
2Cr
2O
7, KIO
3, NaClO, H
2O
2
5 as claim 1 or the polymeric synthetic method of 4 described electroactive aniline, it is characterized in that oxygenant is (NH
4)
2S
2O
8Or FeCl
36H
2O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98108689A CN1088454C (en) | 1998-05-22 | 1998-05-22 | Synthetic method of electroactive large monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98108689A CN1088454C (en) | 1998-05-22 | 1998-05-22 | Synthetic method of electroactive large monomer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1197063A CN1197063A (en) | 1998-10-28 |
| CN1088454C true CN1088454C (en) | 2002-07-31 |
Family
ID=5219754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98108689A Expired - Fee Related CN1088454C (en) | 1998-05-22 | 1998-05-22 | Synthetic method of electroactive large monomer |
Country Status (1)
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|---|---|
| CN (1) | CN1088454C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6627117B2 (en) * | 1998-06-09 | 2003-09-30 | Geotech Chemical Company, Llc | Method for applying a coating that acts as an electrolytic barrier and a cathodic corrosion prevention system |
| CN113248661B (en) * | 2021-06-02 | 2022-06-24 | 甘肃新纪元建材有限公司 | Corrosion inhibition type polycarboxylate superplasticizer and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111664A (en) * | 1994-02-11 | 1995-11-15 | 希巴-盖吉股份公司 | Phthalimidylazo dyes, process for their preparation and the use thereof |
-
1998
- 1998-05-22 CN CN98108689A patent/CN1088454C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1111664A (en) * | 1994-02-11 | 1995-11-15 | 希巴-盖吉股份公司 | Phthalimidylazo dyes, process for their preparation and the use thereof |
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| Publication number | Publication date |
|---|---|
| CN1197063A (en) | 1998-10-28 |
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