CN1018839B - Conductive polymers improved solubility - Google Patents
Conductive polymers improved solubilityInfo
- Publication number
- CN1018839B CN1018839B CN90110251.2A CN90110251A CN1018839B CN 1018839 B CN1018839 B CN 1018839B CN 90110251 A CN90110251 A CN 90110251A CN 1018839 B CN1018839 B CN 1018839B
- Authority
- CN
- China
- Prior art keywords
- thiophene
- formula
- alkoxyl group
- alkyl
- irrelevantly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Abstract
The invention relates to an eigen conductive polymer, the oxidation type in the polymer can be completely dissolved in the normal solvent at ambient temperature, and contains some structural units derived from at least a monomer indicated by formula (I). Wherein R1 is a C6-C30 alkoxy, R2 is a hydrogen atom or a C1-C30 alkoxy. The polymer of the invention is particularly applied to a coating.
Description
The assorted hydrocarbon of known virtue for example can carry out oxypolymerization by anodic oxidation, and generation conductive polymers, these polymkeric substance concerning electrotechnology, aspect semiconductor components and devices, electric switch, shielding material, the solar cell with as electrode materials in electrochemical synthesis and all be significant in reversible charge accumulator.(referring to IBMJRes.Develop.27,330(1983)).
Up to now, the significant drawback of most of known conductive polymerss is that they are not fusible, can not carries out thermoplasticity processing, removes a few exceptions, does not dissolve in common organic solvent.
Minority dopant states can partly soluble conductive polymers still can not be satisfactory at the aspects such as permanent stability, thermostability and film-forming properties of its solvability, conductivity (referring to J.Chem.Soc., Chem.Commun.1985,90 and Synthetic Metals 15,169(1986)).
Also known at last substituted thiophene conductive polymer solution is (referring to the EP-A203 438) that produces by chemical doping process with lysed neutrality (unadulterated) polymkeric substance.But the shortcoming that these solution still exist is must be doped agent and reaction product is polluted with the conductive articles that their are made, and this can bring some detrimentally affects to their later application.
Someone also once proposed can satisfy to a great extent the soluble conductive polymkeric substance (referring to EP-A 257 573) of above-mentioned every requirement, though the described dipole in this place, proton is some application that the solvent of inert not too is suitable for being scheduled to.
Task of the present invention is a kind of purified electro-conductive material of preparation, and they at least can uniform dissolution in several common solvent, and has good film-forming properties and high-temperature stability.
Therefore, the present invention relates to (adulterated) intrinsic conducting polymer of a kind of neutral (non-conductor) and oxidation form, it contains by the monomer shown in formula I, (II), (III) and (IV) and links some structural units that interosculate by 2-position and/or 5-position.By statistical average value, this intrinsic conducting polymer is by following forming: contain the structural unit that at least a monomer derived by shown in the formula I of 60 to 100 moles of % goes out.
(wherein
R
1Be the C of a straight or branched
6-C
30Alkoxyl group, R
2Be a hydrogen atom or a C
1-C
30Alkoxyl group),
Contain the structural unit that at least a monomer derived by shown in the formula II of 0 to 40 mole of % goes out.
(wherein
R
4And R
6Irrelevantly be a hydrogen atom mutually, halogen atom, a C
1-C
12Alkyl, alkoxyalkyl, arylmethyl, aryl, a C
1-C
4Alkoxyl group or O(CH
2CH
2O)
n(CH
3)
nBe 1 to 4), or aromatic ring of the carbon atom that is connected with them formation,
R
3And R
6Irrelevantly be a hydrogen atom mutually, or R
3And R
4And with them continuous carbon atom or R
5And R
6Reach their continuous carbon atoms and respectively constitute an aromatic ring together,
X is a Sauerstoffatom, sulphur atom, NH-base, N-alkyl or a N-aryl),
Contain 0 to 40 mole of % by the structural unit that at least a monomer derived shown in the formula III.
(wherein:
R
7, R
8, R
9And R
10Irrelevantly be a hydrogen atom mutually, C
1-C
12-alkyl, aryl or C
1-C
30-alkoxyl group,
Y and Z irrelevantly are a Sauerstoffatom mutually, sulphur atom, and the NH-base, N-alkyl or N-aryl,
R
11Be an arylidene, inferior heteroaryl or (CH=CH-) conjugated system of p, wherein p is 0,1,2 or 3),
Contain 0 to 40 mole of % by the structural unit that at least a monomer derived shown in the formula IV.
(wherein
R
12And R
13For irrelevantly being a hydrogen atom, halogen atom mutually, C
1-C
12Alkoxyl group, C
1-C
30Alkoxyl group, C
1-C
12Amido, or C
1-C
12-acyloxy,
R
14Be a halogen atom, C
1-C
12-alkyl, C
1-C
30Alkoxyl group, C
1-C
12Amido, C
1-C
12Acyl group or C
1-C
12Acyloxy,
X has the meaning of above-mentioned expression).
The invention still further relates to by at least one monomer shown in the formula I and produce the method for intrinsic conducting polymer as required with the one or more comonomers shown in formula II formula III or (IV) by chemical oxidation or electrochemically oxidative polymerization.
Polymkeric substance of the present invention contains by at least a monomer shown in the following formula I by in the 2-position and/or the binding of the 5-position structural unit of deriving out.
R
1Be the C of a straight chain or a side chain
6-C
30-alkoxyl group is more preferably C
8-C
22-alkoxyl group, particularly C
10-C
16Alkoxyl group,
R
2Particularly a hydrogen atom or C
1-C
30-alkoxyl group is more preferably C
1-C
22Alkoxyl group is C particularly
6-C
12-alkoxyl group.
Representative instance as formula I is:
3-hexyloxy thiophene, 3-oxygen in heptan base thiophene, 3-octyloxy thiophene, 3-oxygen in ninth of the ten Heavenly Stems base thiophene, 3-oxygen in last of the ten Heavenly stems base thiophene, 3-undecane oxygen base thiophene, 3-dodecyloxy thiophene, 3-tetradecyloxyaniline thiophene, 3-pentadecane oxygen base thiophene, 3-n-Hexadecane oxygen base thiophene, 3-octadecane oxygen base thiophene, 3-eicosane oxygen base thiophene, 3-docosane oxygen base thiophene, 3-(2 '-ethyl hexyl oxy) thiophene, 3(2 ', 4 ', 4 '-trimethylpentyloxy) thiophene, 3,4 ,-two hexyloxy thiophene, 3,4-two octyloxy thiophene, 3,4-oxygen base in two ninth of the ten Heavenly Stems thiophene, 3, the two dodecyloxy thiophene of 4-, 3-methoxyl group-4-pentyloxy thiophene, 3-hexyloxy-4-methoxythiophene, 3-methoxyl group-4-oxygen in ninth of the ten Heavenly Stems base thiophene, 3-dodecyloxy-4-methoxythiophene, 3-docosane oxygen base-4-methoxythiophene, 3-oxyethyl group-4-pentyloxy thiophene, 3-oxyethyl group-4-hexyloxy thiophene, 3-butoxy-4-dodecyloxy thiophene, 3-(2 '-second hexyloxy)-the 4-methoxythiophene.
The structural unit number that polymkeric substance of the present invention contains is preferably 8 to 150, and especially 11 to 100.The structural unit number that goes out by at least one monomer derived shown in the formula I, count 60 to 100 moles of % by statistical average value, preferable is 90 to 100 moles of %, 95 to 100 moles of % especially, and this is the structural unit that exists in non-doped polymer.
As monomeric comonomer shown in the formula I, suitable is the monomer shown in formula II formula III and the formula IV.
List the compound shown in the formula II for example at this:
R
4And R
5Irrelevantly be a hydrogen atom mutually, halogen atom, C
1-C
12-alkyl is preferably C
1-C
4-alkyl, an alkoxyalkyl is preferably alkoxy methyl, and an arylmethyl is preferably benzyl or thienyl methyl, and an aryl is preferably phenyl or thienyl, a C
1-C
4-alkoxyl group is preferably C
1-C
2-alkoxyl group or-O(CH
2CH
2O)
nCH
3, and n is 1 to 4, comparatively 1 or 2 or the carbon atom that links to each other with it is common constitutes an aromatic ring, be preferably-phenyl ring, thiphene ring or pyrrole ring.
R
3And R
6Irrelevantly be mutually a hydrogen atom or separately with R
4And R
5The C atom that links to each other with them is common to constitute an aromatic ring, is preferably-phenyl ring, thiphene ring or pyrrole ring.
X is a Sauerstoffatom, sulphur atom, and the NH base, the N-alkyl is preferably N-C
1-C
4-alkyl or N-aryl are preferably the N-phenyl.
That suitable is the pyrroles, 3-chlorine pyrroles, 3-methylpyrrole, 3,4-dimethyl pyrrole, N-methylpyrrole, thianthrene is [3,2-b]-pyrroles also, carbazole, thiophene, 3 methyl thiophene, 3-octyl group thiophene, 3,4-thioxene, 3,4-diethyl thiophene, 3-(methoxyl group ethoxymethyl) thiophene, 3-(methoxy ethoxy ethoxymethyl) thiophene, the 3-methoxythiophene, 3-oxyethyl group thiophene, 3-propoxy-thiophene, 3-butoxy thiophene, the 3-(methoxyethoxy) thiophene, 3-(methoxyl group ethoxy (base) oxyethyl group) thiophene, 3-methoxyl group-4-thiotolene, 3-oxyethyl group-4-thiotolene, 3-butoxy-4-thiotolene, 3-ethyl-4-methoxythiophene, 3-butyl-4-methoxythiophene, 3-dodecyl-4-methoxythiophene, 3,4-dimethoxy-thiophene and thianthrene be [2,3-b]-thiophene also, two thianthrenes are [3,2-b] also; 2 ', 3 '-d] thiophene, dibenzothiophene, isothianaphthene.
In addition, as monomeric comonomer shown in the formula I, can consider the monomer shown in the formula III.
R
7, R
8, R
9And R
10Irrelevantly be a hydrogen atom mutually, C
1-C
12, alkyl is preferably C
1-C
4-alkyl, an aryl is preferably phenyl or thienyl or a C
1-C
30-alkoxyl group is preferably C
1-C
12Alkoxyl group.
Y and Z are a Sauerstoffatom, a sulphur atom, and a NH-base, a N-alkyl is preferably N-C
1-C
4-alkyl or a N-aryl are preferably the N-phenyl.
R " can be arylidene, be preferably phenylene, inferior heteroaryl better is inferior thienyl, furylidene, inferior pyrryl or (CH=CH) p formula system, P is 1,2 or 3.
Especially suitable is 1,2-two-(2-thienyl) ethene, 1,2-two-(3-methyl thianthrene-2-yl) ethene, 1,2-two-(2-furyl) ethene, 1-(2-furyl)-the 2-(2-thienyl) ethene, 1,4-two (2-thienyl)-divinyl 1,3,1,4-two (2-thienyl) benzene, 2,5-two (2-thienyl)-thiophene (special thienyl), 2,5-two (2-thienyl) pyrroles, 2,2 '-two thiophene, 3,3 '-dimethyl-2,2 '-two thiophene, 3,3 '-dimethoxy-2,2 '-two thiophene, 3,4 '-dimethoxy-2,2 '-two thiophene, 4,4 '-dimethoxy-2,2 '-two thiophene, 3,3 '-two hexyloxy-2,2 '-two thiophene, 4,4 '-two dodecyloxies-2,2 ' two thiophene, 3-dodecyloxy-4 '-methoxyl group-2,2 '-two thiophene.
By the structural unit number that monomer derived shown in the formula II goes out, statistical average value is 0 to 40 mole of %, better is 0 to 10 mole of %, and by the structural unit number that monomer derived shown in the formula III goes out, statistical average value is 0 to 40 mole of %, better is 0 to 10 mole of %.
In addition, the end group of polymkeric substance of the present invention can be formed by monomeric structural unit shown in the formula IV, for the polymerization degree and the physicals of improving polymkeric substance can be added the monomer shown in the formula IV in the monomer shown in the formula I to.
R
12And R
13Be mutual incoherent hydrogen atom, halogen atom better is a chlorine or bromine, C
1-C
12-alkyl is preferably C
1-C
4-alkyl, C
1-C
30-alkoxyl group is preferably C
1-C
12-alkoxyl group, C
1-C
12-amido is preferably kharophen or C
1-C
12-acyloxy is preferably acetoxyl group.
R
14Being a halogen atom, better is chlorine and bromine, C
1-C
12-alkyl better is C
1-C
4-alkyl, C
1-C
30-alkoxyl group better is C
1-C
12-alkoxyl group, C
1-C
12-amido better is a kharophen, C
1-C
12-acyl group is preferably ethanoyl or C
1-C
12-acyloxy is preferably acetoxyl group.
X has the above-mentioned meaning of having pointed out.
Examples for compounds shown in the formula IV is the 2-bromothiophene, 2-chlorothiophene, 2-thiotolene; 2-dodecyl thiophene, 2-methoxythiophene, 2-hexyloxy thiophene; 2-dodecyloxy thiophene, 2-kharophen thiophene, 2-bromo-3-methoxythiophene; 2-bromo-4-methoxythiophene, 2-chloro-3 methyl thiophene, 2; the 3-thioxene, 2, the 4-thioxene; 2,3-dimethoxy-thiophene, 2; the 4-dimethoxy-thiophene, 3-methoxyl group-2 thiotolene, 3-hexyloxy-2-thiotolene; 2-methoxyl group-3 methyl thiophene, 4-methoxyl group-2-thiotolene, 2-acetylaminohydroxyphenylarsonic acid 3-methoxythiophene; 2-acetylaminohydroxyphenylarsonic acid 4-methoxythiophene, 2,3; the 4-trimethylthiophene, 3,4-dimethyl-2-methoxythiophene; 2,4-dimethyl-3-methoxythiophene, 3; 4-dimethyl-2-dodecyloxy thiophene, 3,4-dimethoxy-2-thiotolene; 2; 3,4-trimethoxy thiophene, 2-ethanoyl-3; the 4-dimethoxy-thiophene; 2-bromo pyrroles, 2-oxo pyrroles, 2-acetyl pyrrole; 2-chloro-3-methylpyrrole; 2-bromo-3,4-diformazan pyrroles, 2-methyl furan; 2-methoxyl group furans; 2,3,4-trimethylammonium furans.
Because in the locational metalepsy of 2-, compound shown in the formula IV produces chain rupture, chain rupture partly is generally 0 to 40 mole of %, is preferably to be lower than 10 moles of %.
Comonomer shown in above-mentioned formula II, formula III and the formula IV also can use by intermingling, the preparation of the comonomer shown in monomer shown in the formula I and formula II (III) and (IV) is known by prior art, or is described in German patent application P38045222.
Oxidized soluble conductive polymkeric substance will contain a considerable amount of negatively charged ion to offset positive charge, preferably just adds the negatively charged ion of conducting salt or oxygenant in its preparation process.
Suitable negatively charged ion is exemplified below: BF
- 4, PF
- 6, PO
3- 4, AsF
2- 6, SbCl
2- 6, SO
2- 4, HSO
- 4, alkyl SO
- 3, perfluoroalkyl-SO
- 3, aryl-SO
3, F
-, Cl
-, I
- 3, FeCl
- 4Fe[(ON)
6]
3-As not considering that its thermostability also can adopt ClO
4IO
- 4And NO
- 3The present invention preferentially adopts BF
- 4, PF
- 6, CF
3SO
3With right-tosylate.Also above-mentioned anion mixture can be added in the polymkeric substance, adding anion amount is 10 to 30% of monomer unit amount at least, is preferably 15 to 25%.
The manufacturing of polymkeric substance of the present invention is to realize by monomer oxypolymerization, is more preferably by monomeric electrochemistry (anode) polymerization to realize.
For example can work with the comonomer one shown in formula II, (III) and (IV) in case of necessity and make polymkeric substance of the present invention by monomer and the electron acceptor effect shown in the formula I.Suitable oxygenant (it is simultaneously again as polymer-doped dose) has for example I
2, ASF
5, SbCl
5, MOCl
5, FeCl
3, Fe(ClO
4)
3, Fe(BF
4)
3, Fe(CF
3SO
3)
3, to a toluenesulphonic acids iron (III) and a NO
+Salt and NO
+ 2-Salt is as NOBF
4, NOPF
6, NOASF
6, NOSbF
6, NOCF
3SO
3, NO
2BF
4, NO
2PF
6And aryl diazonium salts, for example Tetrafluoroboric acid diazobenzene.
Oxygenant mostly is 2: 1 to 5: 1 greatly to monomeric mol ratio, and as operating in solution, the concentration of oxygenant is generally 0.1 to 0.5 mole/decimeter
3Solvent.
In order to improve the conductive polymers performance of generation, preferably carry out polymerization in the presence of other indifferent salt, because can embed the negatively charged ion that contains in the conductive polymers in salt like this, the salt that can list for example has here: a tetrafluoro borate, hexafluorophosphate, hexafluoro arsenate, hexafluoro antimonate, hexa chloro-antimonate, hydrosulfate, fluorinated alkyl sulfonate is to a tosylate, perchlorate.A tetrafluoro borate preferably, hexafluorophosphate, trifluoromethyl sulfonic acid, the also mixture of available these salt, the positively charged ion of these salt is except alkaline earth metal cation and hydrogen ion, and especially alkalimetal ion is more preferably Li for suitable
+And Na
+Specially suitable (favourable) is R
4N
+Or R
4P
+The type positively charged ion, wherein these R base each uncorrelated mutually be hydrogen, C
1-C
12-alkyl, cycloalkyl or aryl.The negatively charged ion equivalent of being brought into by salt is 0.1 to 100 to the ratio of the negatively charged ion equivalent brought into by oxygenant.
Chemical polymerization can and carry out in emulsion or suspension in monomeric gas phase or liquid phase, but in most of the cases concerning monomer, adopts the organic solvent of non-proton type comparatively favourable, for example acetonitrile, Nitromethane 99Min., propylene carbonate, tetramethylene sulfone, methylene dichloride, chloroform, tetrahydrofuran (THF).Need not oxygenant and be dissolved in the solvent too, but it is comparatively favourable to be dissolved in solvent.
A kind of different chemical polymerization method is to be dissolved in oxygenant in a kind of polymeric matrix or to be suspended in wherein, monomer imports by gas phase, polyreaction is carried out in polymeric matrix then, suitable do polymeric matrix mostly be solubility, can film forming homopolymer or multipolymer, for example Vinyl Acetate Copolymer, polyvinyl alcohol, polymethylmethacrylate, ethylene-vinyl acetate copolymer.Oxygenate content often is 5 to 50 weight % in matrix polymer.
Chemical polymerization at room temperature carries out better, but temperature of reaction can change in a big way, lower limit is not less than the zero pour of one of reaction component, the upper limit is no more than the boiling point or the decomposition point of one of reactive component, great majority are between-60 to 80 ℃, between-20 to 50 ℃, better, generally be that the productive rate that obtains between-10 to 40 ℃ of temperature is the highest.
Particularly advantageous is in electrolyte solvent, having in the presence of the conducting salt, by monomeric anode polyreaction shown in the formula I, in case of necessity and formula II, comonomer polymerization together shown in (III) or (IV) is with electrochemical production polymkeric substance of the present invention.
Form under anode polymeric reaction condition by a kind of usually by stable material for anode, be more preferably by precious metal, particularly by platinum and the gold or by carbon, especially form by RESEARCH OF PYROCARBON, except anode material, used anodic surface and its geometrical shape also are important, because they have the effect of decision to a great extent to the polymerization degree and the performance that generates product, so the option table area greatly and have the electrode of many cavitys to be good.
The anode that is comprising bigger inner spatial volume based on its geometrical shape is specially adapted to the purpose that the present invention will reach, the anode of for example netted, spongy, textile-like, cellular and felt shape, and the product of generation can be deposited in their space.The example of this respect has anode that individual layer and multilayer platinum gauze make or the anode that platinum-rhodium-the alloy silk screen makes, the anode that hard felt and soft felt make, and the anode that makes of individual layer and multilayer carbon fibre fabric.Select anodic to arrange to be parallel to negative electrode for well, when adopting two anodes, two anodes are with the equidistant both sides, negative electrode front and back that are positioned at.
Negative electrode is made up of a kind of current electrode material, for example platinum, gold, nickel, copper, silver, graphite or glass carbon element, be more preferably special steel, can adopt tabular, sheet or netted, generally be to be parallel to anode arrangement, when adopting two negative electrodes, two negative electrodes are with the equidistant both sides, anode front and back that are positioned at, in order to prevent short circuit, an available spacing support of being made up of the inert plastic net separates negative electrode and anode.
For solvable conductive polymers of the present invention can be deposited on the anode with high yield, different with common electrolytic condition, promptly do not need violent stirring, also do not need intensive to shove.By electrolytical interruption stir or slowly successive or interruption flow or electrode slowly continuously or the motion that is interrupted, can impel the monomer mass transfer process that can add the control diffusion to help the anode motion.Dielectric medium velocity of flow for the phase anode can be chosen usually less than 1 cel.The above-mentioned big volume anode that is comprising the space cell of a large amount of electrolysis matter stops because its diffusion distance is short, and helps mass transfer, thereby under stirring and the flow state reaction carried out fully.
The electrochemical polymerization of monomer or monomer mixture is carried out in a kind of common electrolyte solvent system, and this solvent system is stable under the electrochemical polymerization reaction conditions, and to monomer and conducting salt enough solubleness must be arranged.Be preferably with dipolar aprotic solvent, the mixture of acetonitrile, benzonitrile, propylene carbonate, Nitromethane 99Min. and sulfurous gas and these solvents for example, also use other solvent stable under the electrochemical polymerization reaction conditions in case of necessity, dimethyl formamide for example, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), methylene dichloride and tetrahydrofuran (THF).Being less than a kind of polar of 5% as adding to aprotic solvent such as water, methyl alcohol or the acid relevant with conducting salt, is favourable sometimes.
Play the conducting salt of electric charge transfer function in the electrochemical polymerization reaction, their negatively charged ion will be enclosed in the polymkeric substance, and to polymer properties such as thermostability, solvability and electroconductibility are all influential.Can adopt common compound to make conducting salt, a tetrafluoro borate for example, hexafluorophosphate, hexafluoro arsenate, hexafluoro antimonate, hexa chloro-antimonate, hydrosulfate, fluorinated alkyl sulfonate, to a tosylate, perchlorate is wherein with a tetrafluoro borate, hexafluorophosphate and trifluoromethyl sulfonic acid are best, also can adopt the mixture of these conducting salts.
The positively charged ion of conducting salt removes alkaline earth metal cation and H
+Outward, especially suitable is alkali metal cation, is preferably Li
+And Na
+, particularly advantageous is R
4N
+Or R
4P
+The positively charged ion of type, wherein R irrelevantly is hydrogen mutually, C
1-C
12Alkyl, cycloalkyl or aryl, conducting salt consumption between 0.01 to 1 mole, are preferably 0.05 to 0.5 mole/decimeter usually
3Solvent.
To the significant monomer concentration of the polymerization degree of polymkeric substance of the present invention is to have 0.01 to 5 mole in every cubic decimeter of ionogen-solvent, and monomer is preferably 0.05 to 1 mole; In the mixture of comonomer, monomer content shown in the formula I is preferably greater than 80 moles of % generally greater than 60 moles of %, particularly greater than 95 moles of %(for the monomer total amount).
The electrochemical polymerization reaction is preferably at room temperature carried out, but temperature also can change in relative broad range, lowest temperature is not less than the zero pour of ionogen-solvent system, the upper limit is no more than the boiling point of ionogen-solvent system, it in most cases is-60 to 80 ℃, be preferably-20 to 50 ℃, generally can obtain maximum output to 40 ℃ at-10 °.
The time of electrolytic process is depended on used electrolyte system, and the electrolytic condition that is adopted is particularly relevant with the monomeric amount of adding.Usually electrolysis time is 1 to 12 hour, is preferably 2 to 8 hours.
This electrochemical polymerization reaction can or be carried out in the electrolyzer in (electrolysis) groove commonly used, for example gets final product with simple electrolyzer, and it is by an electrolyzer of not separating, and two or more electrodes and a foreign current-power supply are formed.But also can adopt the separation electrolyzer of being with barrier film or ion-exchange membrane or the electrolyzer that has reference electrode, with accurate mensuration electromotive force.It is necessary measuring current draw, because this can estimate used up amount of monomer.In electrolyzer, planar cathode is positioned at the bottom, and the anode of banded shape moves forward by dielectric medium with constant speed or anode is cylindric, and only part is immersed in the ionogen, slowly rolls, and can realize operate continuously like this.
For the electrolyzer that makes enforcement the inventive method turns round, available various direct supplys, but sufficiently high voltage must be provided.Usually 0.1 to 100 volt voltage is adopted in the electrochemical polymerization reaction, is more preferably in 1.5 to 30 volts of scopes and carries out.Proved that favourable current density value is in 0.0002 to 50 milliampere/centimetre than anode surface
2, be preferably at 0.001 to 10 milliampere/centimetre
2Scope.
For from the thick product that chemical polymerization or electrochemical polymerization method obtain, separate and purify soluble polymer (sometimes with anode) as branching carrier availablely do not dissolve this polymer solvent such as water, methyl alcohol, ethanol, in case of necessity also with acetonitrile and pentane washing, conducting salt, monomer and adherent impurity are removed.Then, can dissolve product (sometimes together with the branching carrier) digestion of the solvent of conductive polymers of the present invention with one with above-mentioned preliminary cleaning.Sometimes the impurity that in solution, also have to suspend, available known method such as filtration, centrifugation and method such as pour into are separated them, boil off solvent then, can obtain straight polymer, and by method of the present invention, productive rate is about 50 to 80%.
Can obtain the conductive polymers of powdery or film-type through chemistry or electrochemical oxidation process with substituted thiophene derivant, in contrast, polymkeric substance of the present invention, especially oxidized polymkeric substance, that is doping level be at least 10% conductive polymers can be fully and reversibly be dissolved in many organic solvents.Their structure, performance and range of application are all different with hitherto known conductive polymers.
The solvent that is applicable to polymkeric substance of the present invention is the organic solvent used always or the mixture of solvent.According to the solvent parameter of Hansen, their δ p-value less than the 8.5(card/centimetre
3)
1/2And δ
HValue less than the 6.5(card/centimetre
3)
1/2(referring to Barton, Handbook, of Solubility Parameters and other Cohesion Parameters, CRC Press, 1983,153-161 page or leaf) organic solvent commonly used has for example toluene, dimethylbenzene, naphthane, chlorobenzene, methylene dichloride, chloroform, 1, the 2-ethylene dichloride, 1, trichloroethane, tetrachloroethane, ether, diisopropyl ether, tertiary butyl methyl ether, tetrahydrofuran (THF), the 2-methyltetrahydrofuran, methyl ethyl ketone, diethyl ketone, methyl iso-butyl ketone (MIBK), diisopropyl ketone, diisobutyl ketone, diethylamine, Diisopropylamine, N-BUTYL ACETATE is preferably toluene, o-Xylol, methylene dichloride, special monobutyl methyl ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, methyl iso-butyl ketone (MIBK) and diisobutyl ketone.Can calculate δ-value by the method that document provides during with the solvent mixture that may contain non-solvent.More preferably use δ
PValue is less than 5.5(card centimetre
3)
1/2And δ
HValue less than the 5.0(card/centimetre
3)
1/2Solvent or solvent mixture.Now the 8p value of the solvents that some are suitable for and 8H value are listed following (these S values are at Barton, Handbook of Solubility Parameters and other Cohesion Parameters, CRC Press 1983, lists on the 153-161 page or leaf):
δ-P(card/centimetre
3)
1/2δ-H(card/centimetre
3)
1/2
Toluene 0.7 1.0
O-Xylol 0.5 1.5
Methylene dichloride 3.1 3.0
1 2.1 1.0
Ether 1.4 2.5
Tetrahydrofuran (THF) 2.8 3.9
Methyl iso-butyl ketone (MIBK) 3.0 2.0
Diisobutyl ketone 1.8 2.0
N-BUTYL ACETATE 1.8 3.1
According to different solvents, at per 100 centimetres
3Solubilized at least 0.1 gram conductive polymers is preferably at least 1.0 gram conductive polymerss in the solvent.
It is 10 that the electricity of dissolved polymers is led
-4To 100 Siemens/cm, be preferably 10
-3To 10 Siemens/cm.
The UV/VIS/NIR spectrogram of polymkeric substance shows has the last one to absorb in 400 to 3200 millimicrons of scopes, and being preferably has the last one to absorb in 500 to 1800 millimicrons scope.Polymer thermostable height of the present invention, example confirms that when being heated to more than 200 ℃, its weight loss is 10%.
The difference of polymkeric substance of the present invention and known conductive polymers is on some properties, these properties make the practical application of polymkeric substance of the present invention become possibility, in order to use, but just need solubility and workability or the processing advantage relevant with solubility.What should be mentioned that here is to be coated onto on conductor and the non-conductive material with commercially available mixed with polymers or with certain thickness conductive layer.Can be made into catalyzer, electric switch, semiconductor components and devices, solar cell, shielding material in this way, camouflage coating, surperficial heating unit, electrode special especially can be made into conduction and anlistatig film and fiber and maybe can simplify their manufacturing processed.
The present invention can further specify with following example.Umber that provides in the example of being lifted and percentage ratio, as do not have other explanation are meant weight, and leading than electricity is that four-point assay method with rolled-up stock is measured, and thermal decomposition behavior is measured by differential thermogravimetry (DTG) and dsc (DSC).In example, obtain through the polymkeric substance of purification in the time of 25 ℃ in tetrahydrofuran (THF) solubleness greater than/100 centimetres of 1.0 grams
3The UV/VIS/NIR spectrogram of the tetrahydrofuran solution of polymkeric substance demonstrates strong absorption between 500 and 1800 millimicrons.The molecular-weight average of polymkeric substance of the present invention (weight-average value) is made standard specimen by gel permeation chromatography (GPC) with polystyrene in mesomorphism (unadulterated) and is measured, and this polymkeric substance adopts a platinum cathode to obtain by electrochemical reducing at 0.3 volt (VSAg/AgCl).
Embodiment 1
With 4.34 parts of tetraethylammonium tetrafluoroborates, 4.53 parts of 3-oxygen in ninth of the ten Heavenly Stems base thiophene and 200 parts of acetonitriles are added in the electrolyzer that a band cooling jacket do not separate.Negative electrode is made up of 60 millimeters long and 55 mm wides (senior alloy) V2A-steel disc.(weight per unit area is 0.4 kilogram/meter to adopt the carbonaceous felt of 60 millimeters long, 55 mm wides and 4 mm thick to do anode
2, it is 1.5 meters that the BET method records specific surface
2/ gram), anode is parallel with negative electrode, is fixed on apart from negative electrode 2 centimeters, and the guarantor who makes with polypropylene net separates them apart from support.At electrolysis temperature is 20 ℃, and anodic current is 100 MAHs, and the voltage of electrolyzer is 3 to 6 volts.When the theoretical current amount consumes a half, should be with one of the anode change that is loaded with polymkeric substance new, after the theoretical current amount ran out of, electrolysis finished.The anode that is loaded with crude polymer is put into hexane bath after drying, and repeatedly long-time lixiviate.Being loaded with the carbonaceous felt of polymkeric substance, being placed on lixiviate in the tetrahydrofuran (THF) bath after the drying, enter fully in the solution until polymkeric substance reality, is G with a hole
3Glass filter filter this solution, filtrate is concentrated to dry in rotatory evaporator.Thick product is carried out mechanical disintegration, wash with water, drying, dry again again with the pentane washing, obtain 1.52 parts of blue-black colour band glossy solids.Ultimate analysis provides down column data: 64.3% carbon, 8.4% hydrogen, 13.8% sulphur, 5.4% fluorine.It is 4.8 * 10 that the ratio electricity of product powder product is led
-3Siemens/cm is pressed the analysis of DTG method, observes when being heated to 220 ℃, and weight loss is less than 10%, and measuring not with the GPC method, the molecular-weight average of doped polymer is about 4500.
Embodiment 2
With 4.34 parts of tetraethylammonium tetrafluoroborates, 5.36 parts of 3-dodecyloxy thiophene and 200 parts of acetonitriles add in the electrolyzer of not separating of band cooling jacket, and negative electrode is by 60 millimeters of length, wide 55 millimeters V
2The A steel disc is formed, and with long 60 millimeters, wide 55 millimeters platinized platinum is made anode.At electrolysis temperature is 20 ℃, and anodic current is that to record bath voltage be 3 to 6 volts to 50 MAHs.When the required magnitude of current of theory consumes after 1/4, separate being deposited on the polymkeric substance on the anode and reusing this anode with mechanical means, repeat this method and run out of until the required magnitude of current of theory.Collected thick product adopts mechanical process to pulverize, washes with water, drying, with pentane and acetonitrile washing, carry out drying more again again.Product is collected in the tetrahydrofuran (THF), is G with pore size
3Glass filter filter, with filtrate evaporate to dryness in rotatory evaporator, obtain 1.88 parts of blue-black colour band gloss solids.Ultimate analysis provides following data: 65.7% carbon, 9.0% hydrogen, 11.1% sulphur, 5.3% fluorine.It is 1.5 * 10 that the ratio electricity that product is milled to the powder compression part is led
-2Siemens/cm.Observe when being heated to 255 ℃ weightlessness less than 10% with the DTG method.The DSC method shows in the time of 350 ℃ to be maximum value (130 Jiao Er/gram).Measuring not with the GPC method, the molecular-weight average of doped polymer is 5400.
Embodiment 3
With 4.34 parts of tetraethylammonium tetrafluoroborates, 5.93 part 3-tetradecyloxyaniline thiophene and 200 parts of acetonitriles add in the electrolyzer of not separating of band cooling jacket, negative electrode is that wide 55 millimeters V2A steel disc makes with long 60 millimeters, and anode is to be that 55 millimeters platinized platinum makes with growing 60 mm wides.At electrolysis temperature is 20 ℃, and anodic current is that to record bath voltage be 3 to 6 volts to 50 MAHs.When the theoretical institute magnitude of current consumes after 1/4, separate the polymkeric substance that is deposited on the anode with mechanical means, and reuse this anode.Repeating this method runs out of until the required magnitude of current of theory.Collected thick product adopts mechanical process to pulverize, and washes with water, drying, and is with pentane and acetonitrile washing, dry again again.This product is collected in the tetrahydrofuran (THF), is the glass filter filtration of G3 with pore size, with filtrate evaporate to dryness in rotatory evaporator, obtains 2.04 parts of blue-black colour band gloss solids.Ultimate analysis provides following data: 67.5% carbon, and 10.0% hydrogen, 10.1% sulphur, 4.8% fluorine, it is 1.0 * 10 that the ratio electricity of product powder compression part is led
-2Siemens/cm.
Embodiment 4
3.0 parts of FERRIC CHLORIDE ANHYDROUS are dissolved in 100 parts of acetonitriles, under agitation add 1.0 parts of 3-dodecyloxy thiophene, precipitate fully at 6 hours post polymerization things of stirring at room, filter, and wash with acetonitrile, thick product is dissolved in the tetrahydrofuran (THF), is the glass filter filtration of G3 with hole, and filtrate is evaporated to dried in rotatory evaporator.With pentane and water washing residue and drying, obtain 0.7 part of blue-black colour band gloss solid.Ultimate analysis provides following data: 61.4% carbon, 8.1% hydrogen, 9.9% sulphur, 10.1% chlorine, 4.4% iron.Surveying plain polymkeric substance with the GPC method is made up of the 10-40 monomeric unit more than 90%.It is 4 * 10 that the ratio electricity of product powder compression part is led
-4Siemens/cm is observed when being heated to 200 ℃ product weightlessness less than 10% with the DTG method.
Embodiment 5-9
With 4.34 parts of tetraethylammonium tetrafluoroborates, 3-alkoxy thiophene and 200 parts of acetonitriles add in the electrolyzer of not separating of band cooling jacket.Negative electrode is made by long 60 millimeters and wide 55 millimeters V2A steel disc, and anode is to be 60 millimeters of the length made of platinum/rhodium (95: 5) wire of 0.07 millimeter with diameter, 8 layers of wide 55 millimeters net, at electrolysis temperature is 20 ℃, and anodic current is 100 milliamperes, the time record electrolyzer voltage be 3 to 6 volts.After the theoretical magnitude of current that needs runs out of.Get off with the polymer dissolution that methylene dichloride will be deposited on the anode, solution is the glass filter filtration of G3 by hole, and filtrate is concentrated to dry in rotatory evaporator.Thick product washes with water through mechanical disintegration, and drying is used acetonitrile and hexane lixiviate again, filters then and drying.(table is seen below)
Wherein oxidized form (adulterated) polymkeric substance is dissolved in methylene dichloride, in tetrahydrofuran (THF) and the toluene.
The long-pending amount of monomer monomer (part) polymkeric substance weighing (part) electricity is led (Siemens/cm)
The hot alkoxy thiophene 4.24 0.17 2.10 of 3-
-3
3-alkoxy thiophene in the last of the ten Heavenly stems 4.80 1.10 3.10
-3
3-undecane oxygen base thiophene 5.08 0.51 3.10
-3
3-tridecane oxygen base thiophene 5.44 1.10 2.10
-3
3-pentadecane oxygen base thiophene 6.21 0.28 1.10
-3
Claims (1)
1, (adulterated) intrinsic conducting polymer of neutral (non-conductor) and oxidation form can be used for mixing and be used to conduct electricity with plastics or the coating of non-conducting material, described conductive polymers contains structural unit (I), (II), (III) and (IV) that links to each other and interosculate by 2-position and/or 5-position, by statistical average value, it is made up of following:
Contain the structural unit that at least a monomer derived by shown in the formula I of 60 to 100 moles of % goes out:
(wherein
R ' is a C straight chain or that side chain is arranged
6-C
30-alkoxyl group, and R
2Be a hydrogen atom or C
1-C
30-alkoxyl group)
Contain the structural unit that at least a monomer derived by shown in the formula II of 0 to 40 mole of % goes out:
(wherein
R
4And R
5Irrelevantly be a hydrogen atom mutually, a halogen atom ,-C
1-C
12-alkyl, alkoxyl group, arylmethyl, aryl ,-C
1-C
4-alkoxyl group or O (CH
2CH
2O)
nCH
3, wherein n=1 to 4 or aromatic ring of C-atomic building of linking to each other with them,
R
3And R
6Irrelevantly be a hydrogen atom or R mutually
3And R
4Common carbon atom or the R that links to each other with them
5With R
6The common carbon atom that links to each other with them respectively constitutes an aromatic ring.
X is a Sauerstoffatom, unisulfur stom ,-NH-base ,-N-alkyl or-the N-aryl),
Contain the structural unit that at least a monomer derived by shown in the formula III of 0 to 40 mole of % goes out:
(wherein
R
7, R
8, R
9And R
10Irrelevantly be a hydrogen atom mutually ,-C
1-C
12-alkyl ,-aryl or-C
1-C
30-alkoxyl group,
Y and Z irrelevantly are a Sauerstoffatom mutually, unisulfur stom, and-NH-base ,-N-alkyl or N-aryl,
R " be-arylidene ,-inferior heteroaryl, a formula (CH=CH-) conjugated system of p, wherein P is 0,1,2 or 3),
Contain the structural unit that at least one monomer derived by shown in the formula IV of 0 to 40% mole goes out:
(wherein
R
12And R
13Irrelevantly be a hydrogen atom mutually, a halogen atom ,-C
1-C
12-alkyl ,-C
1-C
30-alkoxyl group ,-C
1-C
12-amido or-C
1-C
12-acyloxy,
R
14Be a halogen atom ,-C
1-C
12-alkyl ,-C
1-C
30-alkoxyl group ,-C
1-C
12-amido ,-C
1-C
12-acyl group or-C
1-C
12-acyloxy,
X has above-mentioned meaning).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3804523A DE3804523A1 (en) | 1988-02-13 | 1988-02-13 | ELECTRICALLY CONDUCTING POLYMERS WITH IMPROVED SOLUBILITY |
| DEP3804523.0 | 1988-02-13 | ||
| CN89100785.7A CN1017052B (en) | 1988-02-13 | 1989-02-13 | Process for prepraing conductive polymers improved solubility |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89100785.7A Division CN1017052B (en) | 1988-02-13 | 1989-02-13 | Process for prepraing conductive polymers improved solubility |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1052488A CN1052488A (en) | 1991-06-26 |
| CN1018839B true CN1018839B (en) | 1992-10-28 |
Family
ID=25742543
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90110251.2A Expired CN1018839B (en) | 1988-02-13 | 1989-02-13 | Conductive polymers improved solubility |
| CN90110252.0A Expired CN1017709B (en) | 1988-02-13 | 1989-02-13 | Process for preparation of improved solubility conductive polymers |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN90110252.0A Expired CN1017709B (en) | 1988-02-13 | 1989-02-13 | Process for preparation of improved solubility conductive polymers |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN1018839B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO311797B1 (en) * | 1999-05-12 | 2002-01-28 | Thin Film Electronics Asa | Methods for patterning polymer films and using the methods |
-
1989
- 1989-02-13 CN CN90110251.2A patent/CN1018839B/en not_active Expired
- 1989-02-13 CN CN90110252.0A patent/CN1017709B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1052488A (en) | 1991-06-26 |
| CN1017709B (en) | 1992-08-05 |
| CN1053618A (en) | 1991-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1025037C (en) | Soluble, electrically conductivepolymers, process for preparing them, and their use | |
| CA1337950C (en) | Polythiophenes, process for their preparation and their use | |
| CN1019304B (en) | Conductive polymers and preparing thereof | |
| EP1551847B1 (en) | 3,4-alkylenedioxythiophene compounds and polymers thereof | |
| US20040074779A1 (en) | Polymeric compositions comprising thieno[3,4-b]thiophene, method of making, and use thereof | |
| CN101293961B (en) | Electrochromic polymeric compounds, preparing method and application thereof | |
| Ashraf et al. | Bulk electropolymerization of alkylpyrroles | |
| US5066731A (en) | Process for modifying electroconductive polymers using ion exchange | |
| CA1311715C (en) | Method for the electropolymerization of conductive polymers | |
| CN1017052B (en) | Process for prepraing conductive polymers improved solubility | |
| CN1014793B (en) | Modified conductive polymers | |
| CN101392173A (en) | Method for preparing co-polymer luminescent material by electrochemical polymerization | |
| CN1018839B (en) | Conductive polymers improved solubility | |
| JPH02218716A (en) | Organic semiconductor and production thereof | |
| JPH03174437A (en) | Electroconductive polymer | |
| CN1350038A (en) | Energy-saving material with far infrared reflecting property and its prepn | |
| JPS6411209B2 (en) | ||
| JPS60203608A (en) | Preparation of electrically conductive polymer | |
| David et al. | Synthesis and Applications of Conducting Polymers–An Overview | |
| Otero et al. | Influence of the electrolyte solution on the electrochemical processability of poly (2, 5-di-(2-thienyl)-pyrrole) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |