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, anti-corrosive paints, because polyaniline is difficult for processing, the defectiveness of molecule own, has therefore limited it and has used widely.
In recent years, started upsurge synthetic and the research polyaniline oligomer both at home and abroad.Human polycondensation methods such as Wudl had synthesized phenyl end capped polyphenyl eight aggressiveness in 1985, it is reported that its electric conductivity and spectrum property and polyaniline are identical.And processing characteristics is better than polyaniline far away.Therefore, some major companies such as IBM have been caused, the very big interest of Unix etc.But because the polycondensation condition of Wudl is very harsh, the today after 10 years, still nobody can repeat out Wudl result then.Recently, the research group of the research group of MacDiarmid and Yen Wei has obtained new breakthrough in the synthetic and application of polyaniline oligomer.It is that benzene one end is the polyaniline tetramer, eight aggressiveness, 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 with several thousand times of polyaniline height.People such as YenWei are raw material with Ursol D and aniline, having synthesized two ends all is the tripolymer of amido, and from tripolymer, synthesized a series of polyaniline oligomer, they have synthesized a series of polymkeric substance with tripolymer, and its corrosion resistance studied, found that its corrosion resistance will be better than polyaniline far away.
Phenyl end capped polyaniline oligomer has very bright application prospect.People's synthetic eight aggressiveness such as Wudl, the electric conductivity of doped hydrochloride are 1.0 Ω
-1Cm
-1, be equal to the electric conductivity of polyaniline.Phenyl end capped polyaniline oligomer is compared with the oligopolymer of other end groups, polyaniline, has the following advantages.The first, to compare with the oligopolymer of Yen Wei with MacDiarmid, phenyl end capped oligopolymer is highly stable, and this helps its processing and use, and self disproportionation reaction easily takes place in air for the above two, becomes complicated product after depositing for some time; Second, compare with polyaniline, there is not defective in the phenyl end capped polyaniline oligomer molecule, its processing characteristics will be better than polyaniline far away, during with other polymer blendings, consistency is better than polyaniline, and the electric conductivity of some phenyl end capped polyaniline oligomers and polyaniline are very approaching again.In a word, phenyl end capped polyaniline oligomer has satisfactory stability, easily process, have consistency preferably with other polymer blending, and some phenyl end capped oligopolymer has very high electric conductivity.
Needing electric conductivity in actual applications is 10
-9-10
-2Ω
-1Cm
-1Material can eliminate static electric charge in travelling belt, carpet, clothes, man-made satellite, Sweet natural gas sleeve pipe.For the electromagnetic shielding material of coating and various case forms, the general requirement electric conductivity surpasses 10
-2Ω
-1Cm
-1, as for the material of making video disc, they are 10 years old
-1Ω
-1Cm
-1Conductive surface, cover with thin dielectric medium, with the oligopolymer of phenyl end capped polyaniline itself, or can satisfy above-mentioned application requiring fully with the material that it and other superpolymer blend obtain.
What especially make us feeling new interest is that in electronic industry, some electronic components need pack with antistatic material in the storage and transport process.At present, because antistatic material does not pass a test, the loss that causes in this respect is very big.Make antistatic material if add metal-powder or carbon black,, need be added to 20-30% and just can reach the conduction stagnation point, film-forming properties and processibility that this will certainly impact polymer according to seepage theory in general-purpose plastics the inside.And the adding conductive polymers only needs to add 2-3% and just can reach the conduction stagnation point.Therefore, if can synthesize the eight phenyl end capped aggressiveness of Wudl in batches, make it and the general-purpose plastics blend, immeasurable market outlook will be arranged in the wrapping material field.
Yet, regrettably, phenyl end capped polyaniline oligomer synthetic but taken a step only difficult in the past few decades, people's such as wudl eight aggressiveness are in 10 years so far thereafter, still nobody can repeat to synthesize, and the method for synthetic eight aggressiveness of people such as wudl, can only synthesize the oligopolymer that phenyl ring is an odd number.And our synthetic route can be synthesized all oligopolymers of phenyl ring from 5 to 99, and the reaction conditions gentleness is simple to operate.
The present invention's polyaniline parent oligopolymer that is in reduction attitude or intermediate oxidation attitude
(wherein n can be 2-76), (for example hydrochloric acid of 1M) uses FeCl under acidic conditions
36H
2O, (NH
4)
2S
2O
8, Ce (SO
4)
2, KMnO
4, KBrO
3, K
2CrO
7, KIO
3, NaClO, H
2O
2, PbO
2, CrO
3, TiCl
4In oxygenant " wherein with FeCl
36H
2O and (NH
4)
2S
2O
8Best " be oxidized to the oligopolymer of high oxidation state, then with
(m=0-20) at DMF (or NMP, DMSO, ethanol, methyl alcohol)-HCl-H
2React in the O system, thus the synthetic phenyl end capped polyphenyl amine oligomer.
Its general formula can be expressed as:
In order to write conveniently, it can be written as the form of going back ortho states:
Characteristics of the present invention are:
1, proposes the synthetic route of an end capped polyaniline oligomer of synthesis of phenyl, can be used for the phenyl end capped polyaniline oligomer of the synthetic various polymerization degree.
2, the present invention will be in go back ortho states or intermediate oxidation attitude polyaniline parent oligopolymer under acidic conditions, be oxidized to the oligopolymer of high oxidation state, then with
(m=0-20) reaction, the synthesis of phenyl end capped polyphenyl amine oligomer.
Above-mentioned tetramer a3.64g (0.01mol) is suspended in to be stirred to system among the hydrochloric acid 250ml of 1mol/L even, adds FeCl
36H
2O5.4g stirs 10min, and suction filtration obtains the salt acid elution b of compound b with 250ml1mol/L, then with pentanoic 1.69g (0.01mol) at 20ml DMF, the 5ml concentrated hydrochloric acid reacts in the 80ml distilled water, obtains phenyl end capped polyphenyl amine oligomer.It goes back the ortho states form:
2: eight aggressiveness of embodiment:
Reaction just changes tetramer a into as above eight aggressiveness c with embodiment 1, and eight aggressiveness c are oxidized to d, with diphenylamine reaction, obtain phenyl end capped polyphenyl amine oligomer then, and it is gone back the ortho states form and is:
Embodiment 3
Reaction just changes pentanoic into embodiment 1
Obtain product, it is gone back the ortho states form and is:
Embodiment 4
Reaction is with embodiment 1, just with 5.4gFeCl
36H
2O changes 2.28g (NH into
4)
2S
2O
4(0.01mol), reaction final product and productive rate there is not influence.