CN100528881C

CN100528881C - Fluorinated alkyl substituted-thieno[3,4-b]thiophene monomers and polymers therefrom

Info

Publication number: CN100528881C
Application number: CN 200610099609
Authority: CN
Inventors: S·赞; G·S·拉尔; W·F·小伯戈因; K·E·明尼克; A·F·诺德奎斯特; L·M·罗伯逊; F·J·沃勒
Original assignee: Air Products and Chemicals Inc
Current assignee: Air Products and Chemicals Inc
Priority date: 2005-05-13
Filing date: 2006-05-12
Publication date: 2009-08-19
Anticipated expiration: 2026-05-12
Also published as: CN1869038A

Abstract

Partially and fully fluorinated alkyl substituted thienothiophene monomers (and polymers thereof) wherein the monomers are represented by the formula: wherein R is a partially or fully fluorinated primary, secondary or tertiary alkyl having from 1 to 8 carbon atoms; and X and X' are independently selected from the group consisting of H, F, Cl, Br, I, MgCl, -COR' , -C CH, and a polymerizable cyclic pi-conjugated carbon-ring structure optionally comprising S, N or O heteroatoms; wherein R' is a primary, secondary or tertiary alkyl having from 1 to 6 carbon atoms, and R' is H or a primary, secondary or tertiary alkyl having from 1 to 6 carbon atoms.

Description

Thieno-[3,4-b] thiophene monomer and polymkeric substance thereof that fluorinated alkyl replaces

The cross reference of related application

[0001] the application is the part continuation application of the common unsettled U.S. Patent application 11/128,538 of 13 submissions May in 2005.The disclosure of application 11/128,538 is hereby incorporated by.

[0002] the application relates to the U.S. Patent application 10/193,598 of submission on July 11st, 2002, is entitled as polymkeric substance of thieno-[3,4-b] thienothiophene and its production and application.Application 10/193,598 relates to the common unsettled U.S. Patent application 10/958,068 of submission on October 4th, 2004, is entitled as the thienothiophene monomers and the conductive polymers of replacement.The disclosure of these applications is hereby incorporated by.

Background technology

[0003] conductive polymers is used in the various photoelectronics application, for example is used for polymer light-emitting diode, solid state illumination device, organic photoelectric pond (photovolatics), advanced memories, organic field effect tube, ultra-capacitor and the electric glimmering light-emitting device of thin-film display.

[0004] polyacetylene is one of conductive polymers that is widely studied the earliest, and finds that polyacetylene shows useful conductivity, and especially after doping, this discovery has caused the sizable interest to other type conductive polymers.

[0005] to have electroconductibility also be known to the thiophene derivant of conjugated poly-(thiophene) and replacement.P-type and n-type doping agent that this polymkeric substance can be cast into film and available routine mix, perhaps with adulterated polymkeric substance casting film correspondingly to improve their electrical characteristic.The cast film that obtains is applicable to various optoelectronic applications.

[0006] US2004/0010115A1, the continuation application of a this part requires the patent application of right of priority, discloses the homopolymer and the purposes of multipolymer in electroactive application that comprise thieno-[3,4-b] thiophene repeating unit.Water-soluble dispersion by this polymkeric substance of ordinary method and multipolymer can be cast so that uniform film to be provided, and this film comprises in electrochromic display device, optical transparent electrode and the antistatic coating having practicality in numerous electroactive application.

[0007] US6,645,401B2 discloses the application of conjugated polymers in semiconductor material and charge transfer material of two thienothiophenes (DTT) with vinylidene or ethynylene linking group, described semiconductor material and charge transfer material comprise field-effect transistor, photocell and transmitter for introduction in photoelectricity and the electronic installation.The polymkeric substance that comprises the DTT that forms by electrochemical polymerization is known, but has proved that in being suitable for preparing the solvent of photoelectricity and electronic installation solvability is restricted and the photocell performance is generally inadequate.

[0008] US6,585,914B2 discloses fluorine carbon functionalized and/or heterocyclic modified poly-(thiophene), especially α, and ω-two perfluoro hexyl joins six thiophene, and described poly-(thiophene) is used to form the film as the n-N-type semiconductorN.These poly-(thiophene) also can be used to form the thin film transistor with FET mobility.

[0009] US6,676,857B2 disclose list with 3-replacement-4-fluorine thiophene polymerized unit-, oligomeric-and polymkeric substance in semi-conductor, charge transfer material, optical electric field effect transistor, photocell and sensor device, be used as liquid crystal material.

[0010] US6,695,978B2 disclose the list of benzo [b] thiophene and dibenzo [b] thiophene-, oligomeric-and polymkeric substance and they in optoelectronic equipment as the application of semi-conductor and charge transfer material.

[0011] US6,709,808B2 discloses the image forming material that comprises conductive polymers, and described conductive polymers is based on thiophen polymer that contains the pyrroles and the polymkeric substance that contains aniline.

[0012] J.P.Ferraris and its colleague has reported the synthetic preparation of the material composition that relates to and its electrology characteristic in " Synthesis and Electronic Properties of Poly (2-phenyl-thieno[3; 4-b] thiophene); Chem.Mater.1999 11,1957-1958 ".

[0013] M.Pomerantz and its colleague discloses solvable low band gaps conductive polymers in " Poly (2-decyl-thieno[3; 4-b] thiophene): a NewSoluble Low-Band Gap Conducting Polymer; Synthetic Materials 84 (1997) 243-244 ", it is poly-that (the 2-decylthiophene is [3,4-b] thiophene and the method for preparing this polymkeric substance also.

The disclosure of the patent that [0014] provides previously, patent application and publication is hereby incorporated by.

Summary of the invention

[0015] the invention provides monomeric substance composition (compositions of matter) that is included in the thienothiophene that has part or all of fluorinated alkyl on 2 and oligopolymer and the polymkeric substance that forms by these thienothiophene monomers polymerizations.This polymkeric substance demonstrates improved processability and electrology characteristic, can be used as hole-injecting material, load transport material and as semi-conductor be used for optics, photoelectricity or electronics, polymer light-emitting diode (PLED), el light emitting device, organic field effect tube (FET or OFET), flat panel display applications (being LCD), RF identification (RFID) label, ultra-capacitor, organic photoelectric pond (OPV), transmitter, based on small molecules or polymkeric substance storing device, electrolytic condenser and as hydrogen storage material.

[0016] part or all of fluorinated alkyl monomer composition of the present invention is expressed from the next:

Formula 1

Wherein

R is part or all of fluorizated primary, the second month in a season or the tertiary alkyl with 1-8 carbon atom; With

X and X ' are independently selected from H, F, Cl, Br, I, MgCl, MgBr, MgI, Sn (R ') ₃,

CH=CHR " ,-OR " ,-COOR " ,-S-COR " ,-B (OR ") ₂,-COR " ,-C ≡ CH and randomly comprise S, N or the pi-conjugated carbocyclic ring structure of the heteroatomic polymerizable ring-type of O;

Wherein

R ' be have 1-6 carbon atom primary, the second month in a season or tertiary alkyl,

And R " be H or have 1-6 carbon atom primary, the second month in a season or tertiary alkyl.

[0017] whole fluorinated alkyl monomer composition of the present invention is commonly referred to as the perfluorination composition, is expressed from the next:

Formula 2

Wherein

R is perfluorination primary, the second month in a season or the tertiary alkyl with 1-8 carbon atom; With

Wherein

R ' be have 1-6 carbon atom primary, the second month in a season or tertiary alkyl and

R " be H or have 1-6 carbon atom primary, the second month in a season or tertiary alkyl.

[0018] in another embodiment, disclose the composition of formula 2, wherein X is that H, X ' are that H and R are perfluorination primary, the second month in a season or the tertiary alkyls with 4 carbon atoms.The composition of formula 2 is provided in another embodiment, and wherein at least one is expressed from the next among X and the X '

With-B (OH) ₂

Formula 3

[0019] in another optional embodiment, the composition of formula 2 is provided, wherein at least one among X and the X ' is selected from F, Cl, Br and I.At least one is Br among preferred X and the X '.

[0020] in another optional embodiment, the material composition of formula 2 is provided, wherein at least one among X and the X ' is-CH=CH ₂

[0021] in another optional embodiment, the material composition of formula 2 is provided, wherein at least one among X and the X ' is-C ≡ CH.

[0022] in another optional embodiment, the material composition of formula 2 is provided, wherein at least one among X and the X ' is Sn (R ') ₃

[0023] in another optional embodiment, the material composition of formula 2 is provided, wherein at least one among X and the X ' is randomly to comprise S, N or the pi-conjugated carbocyclic ring structure of the heteroatomic polymerizable ring-type of O.Preferably, the pi-conjugated carbocyclic ring structure of polymerizable ring-type is formed by randomly comprising the heteroatomic pi-conjugated single carbocyclic ring structure of S, N or O.More preferably, the pi-conjugated carbocyclic ring structure of polymerizable ring-type is formed by randomly comprising heteroatomic 2 or 3 the condensed carbocyclic ring structures of S, N or O.More preferably, at least one among X and the X ' is selected from phenyl, naphthyl, pyrryl, dithienyl, thienyl and their substitutive derivative.Most preferably, at least one among X and the X ' be among thieno-[3,4-b] thiophene or X and the X ' at least one be thieno-[2,3-b] thiophene.

[0024] part or all of fluorinated alkyl polymeric material composition of the present invention (be defined as and comprise dipolymer and oligopolymer) is expressed from the next:

Formula 4

Wherein

R is perfluorination primary, the second month in a season or the tertiary alkyl with 1-8 carbon atom,

N is an integer,

Y is-CZ ¹=CZ ²-,-C ≡ C-phenyl, naphthyl, pyrryl, thienyl, thieno-[3,4-b] thiophene, thieno-[2,3-b] thiophene and their substitutive derivatives separately, Z ¹And Z ²Be independently selected from H, F, Cl or CN.

[0025] the polymeric material composition of formula 4 comprise n wherein be the dipolymer of integer (comprising end value) of 2-10 and oligopolymer and wherein n be 11-50, the polymkeric substance of 000 integer (comprising end value).

[0026] another of formula 4 optional embodiment provides wherein that Y is-material composition of CH=CH-.The optional embodiment of another of formula 4 provides wherein, and Y is-material composition of C ≡ C-.

[0027] in the material composition that the optional embodiment of another of formula 4 provides, Y is selected from phenyl, naphthyl, pyrryl, thienyl, thieno-[3,4-b] thiophene, thieno-[2,3-b] thiophene and their substitutive derivatives separately.

[0028] material composition of formula 4 can be handled with conventional doping agent, for example p-type and n-type doping agent.

[0029] by with one or more material compositions and fluid in conjunction with a material composition prepared composition prose style free from parallelism that can wushu 4, wherein these material compositions can partly or entirely be dissolved in the described fluid of specified rate.The fluid that is fit to comprises water, polyacrylic acid, polymethyl acrylic acid, polymaleic acid, polystyrolsulfon acid, perfluorinated sulfonic acid polymer and polyvinylsulfonic acid, poly-(vinylbenzene-copolymerization-vinyl cyanide) sulfonic acid and its mixture.

[0030] the preferred polymeric material composition of the present invention (be defined as and comprise dipolymer and oligopolymer) is expressed from the next:

Formula 5

Wherein R is that perfluorination primary, the second month in a season or tertiary alkyl and the n with 1-8 carbon atom is 2-50, and 000 integer comprises end value.

[0031] in the material composition that the optional embodiment of another of formula 5 provides, R is trifluoromethyl, perfluor ethyl, perfluoro propyl, perfluoro butyl, 2,2,2-trifluoromethyl-ethyl and 2,2,2-three fluoro-1,1-di-trifluoromethyl ethyl.Preferred R is a perfluoro butyl.

[0032] material composition of formula 5 can be used conventional doping agent for example p-type and the processing of n-type doping agent.

[0033] by with one or more material compositions and fluid in conjunction with a material composition prepared composition prose style free from parallelism that can wushu 5, wherein these material compositions can partly or entirely be dissolved in the fluid described in embodiment of specified rate.

The tool present embodiment

1. definition

[0034] for book and the additional claim of explaining, will provide following term, its implication is as follows:

[0035] the term alkyl is meant the paraffinic hydrocarbons group, and this paraffinic hydrocarbons group can lose a hydrogen atom by alkane and obtain from chemical formula.Non-limitative example is methyl (CH ₃-), ethyl (C ₂H ₅-), propyl group (CH ₃CH ₂C ₂-), sec.-propyl ((CH ₃) ₂CH-).

[0036] the partially fluorinated alkyl of term is meant at least one of alkyl wherein but paraffinic hydrocarbons group that not every hydrogen atom is replaced by fluorine atom.

[0037] the whole fluorinated alkyls of term are meant the paraffinic hydrocarbons group that each hydrogen atom of alkyl is wherein all replaced by fluorine atom.Synonym is a perfluorinated alkyl.

[0038] term halogen is meant in the VIIA family electronegative element (fluorine, chlorine, bromine and iodine) in the periodictable.

[0039] term sulfoxide group (sulfoxyl) be meant have composition RS (O)-group, wherein R is alkyl, aryl, cycloalkyl, perfluoroalkyl or perfluor aryl.Example is including, but not limited to methyl sulfoxide base, phenyl sulfoxide group etc.

[0040] the term alkylsulfonyl is meant and has composition RSO ₂-group, wherein R is alkyl, aryl, cycloalkyl, perfluoroalkyl or perfluor aryl.Example is including, but not limited to methyl sulphonyl, phenyl sulfonyl, p-toluenesulfonyl etc.

[0041] the term acyl group is meant organic acid group, wherein carboxyl-OH replaced by other substituting group (RCO-).Example is including, but not limited to ethanoyl, benzoyl etc.

[0042] the pi-conjugated carbocyclic ring structure of term polymerizable ring-type is meant the single ring architecture that is formed by the optional heteroatoms described in carbon atom and the specification sheets, the perhaps fused rings structure of forming by the optional heteroatoms described in 2 or 3 rings and the specification sheets, wherein the atom in these ring structures is pi-conjugated, causes electron delocalization in the ring structure.The example of single ring architecture is a benzene, and the example of condensed twin nuclei is a naphthalene, and the fused tricyclic example of structure is an anthracene.

[0043] the term fluid is meant and a kind ofly can not forever resists any physical form that causes the mobile shearing force.

[0044] term polymer is meant and has 2-50, the material composition of part or all of fluorinated alkyl thieno-[3, the 4-b] thiophene of 000 repeating unit, a n specification sheets Chinese style 4 and 5 expressions.Term polymer comprises homopolymer, multipolymer, oligopolymer and dipolymer.

[0045] term substrate is meant the sedimentary solid material of a kind of suitable material composition of the present invention (it can be flexible or inflexible).The formation material of substrate can be including, but not limited to glass, organic polymer, plastics, silicon, mineral substance, semiconductor material, pottery, metal etc.Itself can conduct electricity this substrate.

[0046] the electroactive monomer of term be meant can polymerization or copolymerization produce monomer with electricity/characteristic electron polymkeric substance, described electricity/characteristic electron is electroconductibility, semi-conductivity, electroluminescent, electrochromism or photocell characteristic for example.

[0047] be meant can polymerization or copolymerization but can not show monomer in characteristic described in the electroactive monomer definition for the non-electroactive monomer of term.

[0048] the term band gap is meant the energy difference between the electron energy level that is called as conduction band and valence band.

[0049] when being used for the related substances composition, term replaces and to be meant the electron rich that is connected on these material compositions or the group of electron deficiency.The material composition that replaces is also referred to as the derivative of its replacement.

II. describe in detail

[0050] can monomer chain extension of the present invention be formed the polymeric unit so that polymkeric substance to be provided by reacting on position X and X ', this polymkeric substance demonstrates the multiple application described in this specification sheets.According to the general method described in this specification sheets embodiment, do not need the over-drastic test, can prepare the monomer of the formula 1 described in the summary of the invention easily so that the ideal material composition to be provided by replacing the parent material that uses in the suitable embodiment.

[0051] for example, when the monomer X described in the formula 1 and X ' position were hydrogen atom, these monomers can react with the other monomer of the material composition identical with formula 1 and form the homopolymer of polymerized unit.Perhaps, wherein X and X ' are that these material compositions of hydrogen atom can form multipolymers with one or more other electroactive monomers or non-electroactive monomer reactions, comprise Random copolymer RCP, graft copolymer, segmented copolymer and tree structure.

[0052] is fit to be incorporated in the polymkeric substance of the present invention the electroactive monomer that forms multipolymer and comprises that those known in the artly show electroactive monomer, including, but not limited to the thiophene of thiophene, replacement, the thieno-[3 of replacement, 4-b] thiophene, two thieno-s [3,4-b:3 ', 4 '-d] pyrroles, the phenylene of thiophene, pyrroles, thiophthene, replacement, phenylene, naphthalene, naphthalene, biphenyl and the terphenyl of replacement and their the replacement body of replacement, the phenylene vinylidene of phenylene vinylidene and replacement.

[0053] for introduction in the polymkeric substance of the present invention with the substituted thiophene that is fit to that forms multipolymer also [3,4-b] thiophene be expressed from the next:

Wherein primary of R=C1-C12, phenyl, cyclohexyl, naphthyl, hydroxyl, alkyl oxide, carboxylic acid, ester and the sulfonic group of the second month in a season or tertiary alkyl, phenyl and replacement.

[0054] for introduction into comprising United States Patent (USP) 4,959 with the substituted thiophene that is fit to that forms multipolymer in the polymkeric substance of the present invention, the following substituted thiophene of describing in 430 (being hereby incorporated by):

Wherein X C1-C4 alkyl, the C1-C12 alkyl or phenyl representing to replace replace 1,2-vinyl or 1,2-cyclohexenyl.Randomly, alkyl or phenyl can be further by for example replacement such as hydroxyl, ether of functional group.

[0055] for introduction into comprising United States Patent (USP) 4,910 with other the substituted thiophene that forms multipolymer in the polymkeric substance of the present invention, the substituted thiophene that disclosed following formula is represented in 645:

Wherein R1 and R2 are independently selected from H, C1-C4 alkyl, 1,2-cyclohexenyl and phenyl substituted-phenyl.

[0056] if these non-electroactive monomeric existence can be to the electroactive disadvantageous effect that causes of the material composition that obtains, material composition so of the present invention also can comprise can with the non-electroactive monomeric repeating unit of thieno-[3,4-b] thiophene polymeric.

[0057] combining with the fluid described in the content of the present invention by the polymkeric substance (comprising multipolymer and oligopolymer) with needs can be material composition of the present invention as the dispersion utilization.

[0058] dispersion that comprises the polymeric material composition of formula 4 of the present invention and 5 can apply by ordinary method, and described ordinary method comprises that ink jet printing, silk screen printing, wheel change impression brush method (roll to rollprinting), spin coating, liquid level dip coated, spraying, brushing, scraper coating, curtain coating etc.

[0059] consumption that is added into the polymkeric substance (comprising multipolymer and oligopolymer) in solution or the dispersion can change with several factors, and these factors comprise that the molecular weight of material composition and end-use use.The actual amount that adds the material composition of dispersion is easy to be determined, and does not need the over-drastic test.

[0060] can comprise evaporation except that desolvating by the dry dispersion membrane of routine techniques so that needed film to be provided.Dry can at room temperature carry out or the temperature that why not can have a negative impact to gained film character in office under carry out.Yet in order to obtain higher process velocity, film can be dry at elevated temperatures, as long as this temperature can not produce adverse influence to the character of the film that obtains.

[0061] material composition of the present invention can be used in various conventional the application, comprises antistatic coating, conductive coating, electrochromic device, photo-cell assembly, light emitting diode, flat-panel monitor, photoimaging circuit, printed wiring, film crystal device, battery, electric switch, electrical condenser coating, corrosion-resistant coating, electromagnetic shielding, transmitter, LED set lights etc.If necessary, in order to satisfy above-mentioned any demands of applications, by these material compositions that mix with acid doping agent of routine well known in the art (P-doping agent) and basic dopant (n-doping agent), can change the specific conductivity of material composition of the present invention at an easy rate.

[0062] the p-doping agent of Shi Heing comprises mineral acid for example HCl, HNO ₃, H ₂SO ₄, H ₃PO ₄, HBr, HI, organic sulfonic acid is Witco 1298 Soft Acid, lauryl sulfonic acid, camphorsulfonic acid, organic acid dyestuff, methylsulfonic acid, toluenesulphonic acids, poly-sulfonic acid for example poly-(styrene sulfonic acid) and multipolymer for example, carboxylic acid is for example polyacrylic acid, polymaleic acid of hexanodioic acid, nonane diacid, oxalic acid and polymeric poly carboxylic acid for example, polymethyl acrylic acid and comprise these sour multipolymers.Conventional mixing and doping agent for example mineral acid/organic acid also can be used to give material composition ideal of the present invention electroactive characteristic.

[0063] though usually preferred P-doping agent also can come the n-material composition of the present invention that mixes with conventional basic dopant, basic dopant is including, but not limited to Na, K, Li and Ca.

[0064] formula 4 of the present invention and 5 material composition are very suitable for preparing some assembly of photodiode (LEDs).Usually LEDs has multilayer, comprises substrate and tin indium oxide (ITO) anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode.The indium-tin oxide anode that p-dopant composition of the present invention is particularly suitable for replacing LED.P-dopant composition of the present invention also is especially suitable for use as the hole injection layer of LED.Not dopant composition of the present invention can be used in hole transmission layer, luminescent layer and/or the electron transfer layer of LED.

[0065] mixture of material composition of the present invention and other electroactive material also is included among the present invention, and described other electroactive material is laser dyes, other electroactive polymer, the hole transport that comprises electroactive organometallic compound or electron transport material for example.

[0066] photo-cell assembly and LEDs have special similarity.Light (for example sunlight) thus input on device, produced voltage difference and produced electric current, rather than voltage be applied to be LED matrix generation light on the device.The layer of LED and photo-cell assembly is similar but is not equal to.Light catches organism or polymkeric substance comprises the middle layer, and this middle layer has the hole transport/electron transfer layer that randomly is placed between negative electrode and the anode.Material composition of the present invention can or be used in light as negative electrode and hole injection layer (adulterated) and catch (unadulterated) in the layer.

[0067] material composition of the present invention can be used to prepare electrochromic device, and when voltage was applied on the base material well known in the art, electrochromic device allowed or stops light by transparent base material.Other application of material composition of the present invention comprises electromagnetic shielding and dim light mirror (dimmable mirrors).

[0068] dopant composition of the present invention can be used as antistatic coating, and it is by on the base material of enumerating from the aqueous solution or organic solvent solution or dispersion paint definitional part.This antistatic coating can comprise and other mixture of polymers, comprises emulsion, thereby obtains conductivity and for example be bonded in the balance of the film properties on the suitable substrate.Material composition of the present invention also can be as the coating or the additive that can make extensive stock conduction, and described commodity comprise the various base materials that are used for antistatic coating and electro-plating method, printed wiring, photoimaging circuit, semiconductor device etc. of above record.

[0069] though the preferred embodiment of the invention relates to material composition is used as transparent/electro-conductive material, but believed also based on the conduction opaque coating of material composition of the present invention can be used in the special applications that transparency is unessential and electroconductibility is important in the described special applications.Some application examples such as antistatic coating may need painted, and this will cause the application of loss of clarity and various electric conduction paints.Utilize the printed wiring of these materials also not require transparency usually.

[0070] material composition of the present invention also can be used to prepare optically transparent conductive coating, and this conductive coating is used in optical transparent electrode, electrically conducting transparent binding agent, camouflage coating, transparent EMF shielding, touch-screen, flat-panel monitor, moves the plain aerial of using, transparent condenser coating etc.

[0071] in order to improve electroconductibility, additive is ethylene glycol, glycol ether, N.F,USP MANNITOL, 1 for example, ammediol, 1,4-butyleneglycol, N-Methyl pyrrolidone, sorbyl alcohol, glycerol, propylene carbonate and other high boiling point organic compound that is fit to be introduced in the dispersion of material composition of the present invention.

[0072] other additive comprises for example granular copper of conductive filler material, silver, nickel, aluminium, carbon black etc.Dielectric filler is talcum powder, mica, wollastonite, silica, clay, TiO for example ₂, dyestuff, pigment etc. also be introduced in the dispersion so that promote specified property, for example modulus of Zeng Jiaing, surface hardness, surface color etc.

[0073] when the needs special applications, the dispersion of material composition of the present invention also can comprise antioxidant, UV stablizer and tensio-active agent.In dispersion, add tensio-active agent normally for control stiffness, surface tension and surperficial wetting properties.The sliding property agent in preferred surface comprises acetylenediol.For specific end-use, also can in this dispersion, add viscosity modifier (for example associative thickeners) to adjust viscosity.

[0074] material composition of the present invention can prepare easily by several different methods.Material composition of the present invention preferably utilizes aqueous polymerization method preparation, and wherein required thieno-[3,4-b] thiophene, polyanion and oxygenant react being enough in the presence of the water form under the reaction conditions of emergencing copolymer mutually.It is unimportant to carry out the polymeric temperature, but can influence rate of polymerization.

[0075] temperature range that comprises of typical reaction conditions is 0 ℃-about 50 ℃.Polymerization will continue for some time up to reaction and finish the polymerization degree that reaches required.The polymerization degree is not an important factor of the present invention, but can and change along with the end-use application.The required polymerization degree depends on end-use, and it does not need the over-drastic test to be determined by those of ordinary skills at an easy rate.The polymeric time range is that several minutes arrives about 48 hours, and depends on several factors, comprises the oxygenant that uses in size, polymerization temperature and the polymerization process of the reactor that uses in the polyreaction.

[0076] in aqueous solution polymerization method, the consumption of polyanion and oxygenant can vary widely, and does not need undue experimentation can be determined for any given polyreaction.For example, the weight ratio scope of monomer of the present invention and required polyanion is 0.001-50 normally, preferred 0.05-2.0.The weight ratio scope of monomer of the present invention and required oxygenant is 0.01-10 normally, preferred 0.1-2.0.Under the situation of ferric sulfate, the monomeric amount ranges of the present invention is 0.1-5.

[0077] polyanion of Shi Heing comprises poly carboxylic acid, and for example (NAFION is E.I.Dupont de Nemours﹠amp for polyacrylic acid, polymethyl acrylic acid, NAFION, perfluorinated sulfonic acid polymer; CO., the registered trademark of Wilmington Delaware), the negatively charged ion of polymaleic acid and poly-sulfonic acid such as polystyrolsulfon acid and polyvinylsulfonic acid.Poly carboxylic acid and poly-sulfonic acid also can be that vinyl carboxylic acid and vinyl sulfonic acid are with other monomer such as acrylate and cinnamic multipolymer.The preferred molecular weight range that the acid of polyanion is provided is 1,000-500, and 000, preferred 2,000-500,000.The acid that polyanion is provided is commercially available or can prepares according to currently known methods.

[0078] oxygenant of Shi Heing comprises iron (III) salt, for example FeCl ₃, Fe (ClO ₄) ₃With organic acid and comprise iron (III) salt of the mineral acid of organic residue, H ₂O ₂, K ₂Cr ₂O ₇, over cure soda acid or ammonium, peroxyboric acid alkali, potassium permanganate and mantoquita be Tetrafluoroboric acid copper for example.In addition, iodine, air and oxygen can be advantageously used for oxygenant.Preferred persulphate and organic acid and bag have iron (III) salt of the mineral acid of machine residue, because they do not have corrodibility.

[0079] example of organic acid iron (III) salt is Fe (III) salt of C1-30 alkylsulphonic acid, for example methylsulfonic acid or dodecane sulfonic acid; Aliphatics C1-20 carboxylic acid, 2-ethylhexyl carboxylic acid for example, aliphatics perfluorocarboxylic acid, for example trifluoroacetic acid and Perfluorocaprylic Acid; Aliphatic dicarboxylic acid is the sulfonic acid that replaces of oxalic acid and aromatic, optional C1-20 alkyl for example, for example the mixture of Phenylsulfonic acid, tosic acid and Witco 1298 Soft Acid and aforementioned organic acid Fe (III) salt.The example that wraps iron (III) salt of the mineral acid with machine residue is iron (III) salt of the sulfate hemiester of C1-20 alkanol, for example iron of lauryl sulfate (III) salt.

[0080] the another kind of method that optionally prepares polymkeric substance of the present invention of the present invention is an electrochemical process, the polymerization in the electrochemical cell that uses the configuration of three electrodes of wherein required monomer.The three electrodes configuration that is fit to comprises a button working electrode that is selected from platinum, gold and vitreous carbon button working electrode, the reference electrode of a platinum bar counter electrode and the non-water of Ag/Ag+.The ionogen that is fit to is selected from tetrabutylammonium perchlorate/acetonitrile, trifluoromethanesulfonic acid (triflate) lithium/acetonitrile and tetrabutyl ammonium hexafluorophosphate/acetonitrile.

[0081] the conventional electrolysis battery can be used to implement to prepare the electrochemical method of material composition of the present invention.Preparing the preferred working electrode of material composition of the present invention is that glassy carbon electrode and preferred ionogen are tetrabutylammonium perchlorate/acetonitriles.

[0082] in the presence of sodium polystyrene sulfonate, use the polymerization of ring volt-ampere, monomer of the present invention also can be by electrochemical polymerization.Shown in the increase of current-responsive in than the suboxide reduction process, polymerization is significantly, and described redox processes is corresponding to by the reduction and the oxidation of the conductive polymers of galvanic deposit on electrode surface.After the electrochemical polymerization, electrode is shifted out from ionogen, use normal saline washing, put it into the NaCl/H of 0.5M then ₂In the O solution.

[0083] in the aqueous solution, utilize polystyrolsulfon acid or perfluorinated sulfonic acid polymer as polyanion, ammonium/persulphate and/or ferric sulfate (III) are carried out preferred oxypolymerization method as chemical oxidizing agent.

[0084] polymerization has been described as homopolymerization, but also may carry out monomer required for the present invention and another kind of monomer for example 3,4-ethylidene dioxy thiophene or pyrroles's copolyreaction.

[0085] for example, can Synthetic 2-(perfluoro butyl)-thieno-[3,4-b] thiophene by 5 footworks.

[0086] after monomer forms, forms many X and X ' and be not each monomeric derivative of H.In the reaction of back, one or two hydrogen atom can be replaced by other functional group.Selectively, the part derivative can be by earlier being converted into its derivative with thiophene from the beginning, carry out then the chemical described in the X and X and above-mentioned 1-5 step wherein compatible 5 go on foot reactions steps.

[0087] polymkeric substance of the present invention comprises unregulated polymer and regional rule polymkeric substance.The regional rule polymkeric substance is meant that polymerized unit connects with from beginning to end, that is to say, 6 of first polymerized unit are connected on 4 of second polymerized unit, and 6 of second polymerized unit are connected unitary 4 of trimerization and go up or the like.

[0088] 2-(perfluoro butyl)-thieno-[3,4-b] polymerization of thiophene monomer can utilize the aqueous polymerization method to realize, 2-(perfluoro butyl)-thieno-[3 wherein, 4-b] thiophene monomer, polyanion and oxygenant be enough to form for example reaction conditions reaction down of poly-(2-(perfluoro butyl)-thieno-[3,4-b] thiophene) of homopolymer in the presence of water.Can the polymerization and the formed polymkeric substance that mixes in one step by this polymerization process.

[0089] amount of polyanion that uses in the aqueous polymerization method and oxygenant can change in wide region, and does not need undue experimentation just can determine the amount of polyanion and oxygenant in the arbitrarily given polymerization.For example, the weight ratio scope of 2-(perfluoro butyl)-thieno-[3,4-b] thiophene monomer and required polyanion is 0.001-50 normally, preferred 0.05-2.0.The weight ratio scope of 2-(perfluoro butyl)-thieno-[3,4-b] thiophene monomer and required oxygenant is 0.01-10 normally, preferred 0.1-2.0.For example, when ferric sulfate was used as oxygenant, the amount ranges of 2-(perfluoro butyl)-thieno-[3,4-b] thiophene was 0.1-5.To use the variation of monomer ionization potential in order solving, can to change the character of oxygenant.Known various Fe (II)/Fe (III) couplet demonstrates different electromotive forces, for example EeCl according to their parts separately ₃Fe ₂(S ₂O ₈) ₃Fe (phen) ₃Use more weak oxygenant if desired, then can consider couplet based on copper.Use stronger oxygenant if desired, then can consider couplet based on cobalt.

[0090] by using the common metal catalytic polymerization of describing in the open source literature, the monomer described in this specification sheets formula 1 can be aggregated.According to X and the substituent character of X ', those of ordinary skills can change condition, so that produce required polymkeric substance under the condition that does not need undue experimentation.

[0091] after each monomer polymerization, the film of polymkeric substance of the present invention can mix with conventional p-and n-type doping agent.The doping process generally includes with oxygenant or reductive agent and handle the film semiconductor material in redox reaction, and to form delocalization ion center in described material, corresponding counter ion are from used doping agent.For example, adulterating method comprises in atmosphere or under the decompression, carries out electrochemical doping with the doping steam exposure in comprising the solution of doping agent, doping agent is contacted with the semiconductor material for the treatment of dissipation of heat, and dopant ion is moved in the semiconductor material.

III. embodiment

[0092] providing following examples is that each embodiment and as a comparison is described for example, rather than to the qualification of invention scope.

Embodiment 1

The preparation of 2-(perfluoro butyl)-thieno-[3,4-b] thiophene

[0093] prepares 2-(perfluoro butyl)-thieno-[3,4-b] thiophene with described method by 5 footworks.

Step 1

The preparation of 3-bromo-4-(trimethyl silyl ethynyl) thiophene

[0094] on 2 liters three-necked round bottom flask, is equipped with reflux exchanger, mechanical stirrer and thermopair, uses the exsiccant nitrogen purging then.Then, pack in the flask 240g diethylamine (in advance through the KOH bead dry and filter), 387.04g (1.60mol) 3,4-dibromo thiophene, 800mg (3.04mmol) triphenylphosphine, 600mg (5.48mmol) cupric iodide (I) and 78.56g (0.80mol) part trimethyl silyl acetylene.The mixture that stirs is warming up to 40 ℃.Two (triphenylphosphine) palladiums (II) of dichloro that add 2.00g (2.8mmol) then.Under mechanical stirring and atmosphere of static nitrogen layer, will be reflected at 40 ℃ and keep 4 hours.When reaction mixture is considered to finish, reaction mixture is cooled to room temperature.

[0095] by reaction mixture being positioned on the rotatory evaporator and evaporation is removed diethylamine and reclaimed product 3-bromo-4-(trimethyl silyl ethynyl) thiophene.600ml pentane and 40g activated carbon (Darco, 12-20 order) are added in the residue after the evaporation together.Then, filter pentane solution by silicagel column (100g) and remove palladium, subsequently with 600ml or more pentane.Remove the pentane solvent of collecting in the solution by evaporation on rotatory evaporator.The quality of isolated thick product approximately is 316g, comprises 142g 3-bromo-4-(trimethyl silyl ethynyl) thiophene.Remaining material is produced 3-bromo-4-(trimethyl silyl ethynyl) thiophene (productive rate based on trimethyl silyl acetylene is 60.3%) of 129g 97.2% by vacuum distilling.BP?37℃，740mtorr。 ¹H-NMR：δ(ppm)0.3(s)，7.19，7.45； ¹³C-NMR：δ(ppm)-0.1，97，113，122，123，129。

Step 2

The preparation of 3-bromo-4-thiophene acetylene

[0096] according to following reaction formula the product of step 1 is converted into 3-bromo-4-thiophene acetylene:

[0097] (10g 38mmol) and THF (45ml), stirs and is cooled to 2 ℃ with 3-bromo-4-(trimethyl silyl ethynyl) thiophene.Slowly add tetrabutyl ammonium fluoride (75ml 1M is in THF), maintain the temperature at 0 ℃-5 ℃.After interpolation is finished, the reactant stirring was heated to reactant 20 ℃ in 30 minutes simultaneously.In flask, add entry (140ml), and stirred product 2 hours down at 20 ℃.Then, with 3 * 50ml hexane lixiviate product.HCl with 40ml 10% washs the hexane extractive substance that merges, and washes with water then, again through dried over mgso.Except that after desolvating, reclaim the orange liquid product by rotary evaporation.After distillation, reclaim 6.5g 3-bromo-4-thiophene acetylene (92% productive rate).Bp?58℃，1.5mm?Hg。 ¹H-NMR：δ(ppm)7.4，7.5，7.7； ¹³C-NMR：δ(ppm)77，82，114，124，125，134。

Step 3

3-bromo-4-(1-iodo-2-perfluoro butyl-vinyl) thiophene) preparation

[0098] (4.1g, 22mmol) (15.16g 44mmol), and is cooled to 15 ℃ with the perfluoro butyl iodide to stir 3-bromo-4-thiophene acetylene in the mixture of acetonitrile (80ml) and water (50ml).In solution, add then sodium bicarbonate (2.4g, 29mmol) and sodium bisulfite (4.5g, 26mmol).Stir after 20 minutes, water (75ml) diluting reaction thing is also used the pentane lixiviate.From product, remove pentane by rotary evaporation, isolate about 10g crude mixture.MS：m/z?407，405，207，188，157，127，69； ¹H-NMR：δ(ppm)6.7(t，1)，7.22(d，1)，7.27(d，1)； ¹⁹F-NMR：δ(ppm)-80(s，3)，-107(s，2)，-124(s，2)，-126(s，2)。

Step 4

The preparation of 3-bromo-4-(perfluoro butyl ethynyl)-thiophene

[0099] (7g 175mmol) is dissolved in the mixture of 50/50 second alcohol and water, and then joins in the separated product of step 3 with sodium hydroxide.Stirring reactant under the room temperature spends the night.With pentane lixiviate product, then at 41 ℃, distillation purifying under the 300mTorr.MS?m/z?406，404，386，384，237，235，169，156，119，111，69； ¹H-NMR：δ(ppm)7.3(d，1)，7.8(d，1)； ¹⁹F-NMR：δ(ppm)-80(s，3)，-97(s，2)，-124(s，2)，-126(s，2)。

Step 5

The preparation of 2-(perfluoro butyl)-thieno-[3,4-b] thiophene

[0100] according to following reaction formula the product of step 4 is converted into 2-(perfluoro butyl)-thieno-[3,4-b] thiophene:

[0101] mixture of 155ml diethyl ether and 9.45g 3-bromo-4-(perfluoro butyl ethynyl)-thiophene (0.0233mol) is put into the flask of 500ml round bottom three necks, flask is equipped with thermometer, gas inlet, magnetic stirring rod, pneumatic outlet and diaphragm seal mouth.After solution is cooled to-73 ℃, replace air in the flask fully with nitrogen.

[0102] keeping temperature of reaction to be lower than in-70 ℃, in 5 minutes, adds the solution of 9.5ml 2.5M n-Butyl Lithium in hexane through barrier film with syringe.Adding n-Butyl Lithium after 25 minutes, keeping temperature of reaction, the Powdered sulphur of 0.761g exsiccant (0.0238mol) is in seconds being added at-72 ℃ to-75 ℃.After 1 hour, when being lower than-72 ℃, approximately-50 ℃ 155ml methyl alcohol joined in the reaction mixture, and in about 1 hour, reactant is heated to room temperature.At 35 ℃ of solvents of removing in the reactant.

[0103] residue is suspended/be dissolved in the 155ml hexane, be cooled to-78 ℃ under the condition of nitrogen gas, in 1 minute, add the 10ml2.5M n-Butyl Lithium.After 30 minutes in, mixture heating up to-50 ℃, and was kept 30 minutes at-50 ℃ again.Finish lithiumation by adding 155ml methyl alcohol.Remove at 35 ℃ and to desolvate, in the 50ml diethyl ether that residue suspended/be dissolved in.Solid is removed by centrifugal, again with twice of ether flushing.The combined ether extractive substance produces the solution that comprises 5.7g 2-(perfluoro butyl)-thieno-[3,4-b] thiophene, and removes ether at 35 ℃.

[0104] use the room temperature receptor that product is carried out Kugelrohr distillation (55 ℃ of jar temperature).In 50-56 ℃ of oil bath, distilling distillment once more on the short-path distillation device.3.0g heart cut comprises 97.2%2-(perfluoro butyl)-thieno-[3,4-b] thiophene (35.4% isolated yield).36 ℃ of BP, 160mtorr; MS m/z 358,189,359,339, and 191,360,220; ¹H-NMR (CDCl ₃): δ (ppm) 7.3 (s, 2), 7.6 (s, 1); ¹³C-NMR: δ (ppm) 111 (s, 1), 116 (s, 1), 120 (s, 1), 135t, 1), 138 (s, 1), 145 (s, 1); Multiplet is 106,108, and 110,112,114,116,118 (4); ¹⁹F-NMR: δ (ppm)-82 (s, 3) ,-105 (s, 2) ,-123 (s, 2) ,-127 (s, 2).

Embodiment 2

The preparation of 3-bromo-4-(1-iodo-2-trifluoromethyl-vinyl) thiophene

[0105] with 3-bromo-4-thiophene acetylene (4.0g, 22mmol), (2.5g 29mmol) packs in the 300cc Stainless Steel Pa Er reactor for acetonitrile (60ml), water (20ml) and sodium bicarbonate.Solution is cooled to-35 ℃ and the degassing.Trifluoromethyl iodide (26mmol) is compressed in the reactor.(4.6g 26mmol) is dissolved in the water (20ml), joins then in the reactor, stirs 2 hours with sodium bisulfite.Other trifluoromethyl iodide (26mmol) compression is advanced in the reactor, stirred 1 hour.The dilute with water reactant, and use the pentane lixiviate.Utilize rotary evaporation from product, to remove pentane.MS：m/z?384，382，284，257，255，176，157，127，107，69。

Embodiment 3

The preparation of 3-bromo-4-(trifluoromethyl ethynyl) thiophene

[0106] (1.2g 30mml) is dissolved in the mixture of 50/50 second alcohol and water, joins then in the product of embodiment 2 with sodium hydroxide.Reaction stirred is spent the night under the room temperature.With pentane lixiviate product, then at 25 ℃, distillation purifying under the 300mTorr.MS：m/z?256，254，236，234，206，204，175，131，106，99，69； ¹H-NMR：δ(ppm)7.3(d，1)，7.7(d，1)； ¹⁹F-NMR：δ(ppm)-50(s，3)。

Embodiment 4

The electrochemical polymerization of 2-(perfluoro butyl)-thieno-[3,4-b] thiophene

[0107] 2-(perfluoro butyl)-thieno-[3,4-b] thiophene is dissolved in reaches the 10mM monomer concentration in 100mM tetrabutyl ammonium hexafluorophosphate/anhydrous acetonitrile and use 3-electrode configuration to carry out electrochemical polymerization, an ITO working electrode (1cm is used in this configuration ²Delta Technologies, limited, R _s=5-15Ohm, CG-50IN-CUV), platinum thin plate counter electrode (1cm ²) and the non-water reference electrode of Ag/Ag+.This reference electrode (Bioanalytical Systems, Inc.; MF-2062) by at 0.1M AgNO ₃Silver-colored lead in the anhydrous acetonitrile is formed.CH Intruments Model 700B Series Electrochemical Analyzer/Workstation is used in and drives electrochemical polymerization under the room temperature nitrogen blanket.Applied voltage circulates between 1.6V and 0V with the speed of 100mV/sec.

[0108] from the formation of transparent ITO electrode surface blue film as can be seen polymerization be tangible.

Embodiment 5

Poly-(2-perfluoro butyl)-thieno-[3,4-b] thiophene) electrochemical synthesis

[0109] with 2-(perfluoro butyl)-thieno-[3,4-b] thiophene is dissolved in the monomer concentration that reaches 10mM in 100mM tetrabutyl ammonium hexafluorophosphate/anhydrous acetonitrile, and using 3-electrode configuration carrying out electrochemical polymerization, an ITO working electrode (1cm is used in this configuration ², Delta Technologies, limited, R _s=5-15Ohm, CG-50IN-CUV), platinum thin plate counter electrode (1cm ²) and the non-aqueous reference electrode of Ag/Ag+.This reference electrode (Bioanalytical System, Inc.; MF-2062) by at 0.1MAgNO ₃Silver-colored lead in the anhydrous acetonitrile is formed.CH Intruments Model 700B Series ElectrochemicalAnalyzer/Workstation is used in and drives electrochemical polymerization under the room temperature nitrogen blanket.It is constant that applied voltage remains on 1.4V 30 seconds.

[0110] from the formation of transparent ITO electrode surface blue film as can be seen polymerization be tangible.

Embodiment 6

2-(perfluoro butyl)-thieno-[3,4-b] thiophene and 3, the copolymerization of 4-ethylidene dioxy thiophene

[0111] preparation except a kind of solution is by 5mM 2-perfluoro butyl in 0.1M tetrabutyl ammonium hexafluorophosphate (TBAPF6)/ACN)-thieno-[3,4-b] outside thiophene and 5mM ethylidene dioxy thiophene form, 2-(perfluoro butyl)-thieno-[3,4-b] thiophene and 3, the multipolymer of 4-ethylidene dioxy thiophene is according to embodiment 4 described method preparations.Find that than the increase of electric current in the suboxide reduction process and the initial oxidation effect that utilizes cyclic voltammetry to measure the multipolymer that forms polymerization is tangible by continuous sweep.Multipolymer shows relative Ag/AgNO ₃-the 0.5V starting voltage.(electrochemical synthesis poly-(3,4-ethylidene dioxy thiophene) has-0.65V starting voltage)

[0112] has the unusual 2-of negativity HOMO level (perfluoro butyl)-thieno-[3,4-b] thiophene monomer and can be used in the lithium rechargeable battery of non-water additive as additives for overcharge protection.Avoid overcharging in order to protect battery to make it, this additive must can carry out polyreaction.In the process of overcharging, when voltage surpasses the maximum battery voltage of battery permission, the additive polymerization reaction take place.Having very, the monomer of negativity HOMO level is ideally suited this application.

[0113] essential characteristic of the present invention all is described in above-mentioned disclosure.Those skilled artisans will appreciate that and do not departing from the present invention's spirit and do not changing following claim scope and be equal under the situation of replacement, can make various modifications the present invention.

Claims

1, the compound represented of following formula:

Wherein

R is part or perfluorination primary, the second month in a season or the tertiary alkyl with 1-8 carbon atom; With

Wherein

2, the compound of claim 1, wherein R is perfluorination primary, the second month in a season or the tertiary alkyl with 1-8 carbon atom.

3, the compound of claim 2, wherein X and X ' are that H and R are perfluorination primary, the second month in a season or the tertiary alkyls with 4 carbon atoms.

4, the compound of claim 2, wherein at least one is expressed from the next among X and the X ':

With-B (OH) ₂

5, the compound of claim 2, wherein at least one is selected from F, Cl, Br and I among X and the X '.

6, the compound of claim 2, wherein at least one is Br among X and the X '.

7, the compound of claim 2, wherein at least one is-CH=CH among X and the X ' ₂

8, the compound of claim 2, wherein at least one is-C ≡ CH among X and the X '.

9, the compound of claim 2, wherein at least one is Sn (R ') among X and the X ' ₃, R ' be have 1-6 carbon atom primary, the second month in a season or tertiary alkyl.

10, the compound of claim 2, wherein at least one is randomly to comprise S, N or the pi-conjugated carbocyclic ring structure of the heteroatomic polymerizable ring-type of O among X and the X '.

11, the compound of claim 10, wherein the pi-conjugated carbocyclic ring structure of polymerizable ring-type comprises S, N or the heteroatomic pi-conjugated single carbocyclic ring structure of O is formed by optional.

12, the compound of claim 10, wherein the pi-conjugated carbocyclic ring structure of polymerizable ring-type comprises S, N or heteroatomic two or three the pi-conjugated condensed carbocyclic ring structures of O are formed by optional.

13, the compound of claim 10, wherein at least one is selected from phenyl, naphthyl, pyrryl, dithienyl, thienyl among X and the X '.

14, the compound of claim 10, wherein at least one is thieno-[3, a 4-b] thiophene among X and the X '.

15, the compound of claim 10, wherein at least one is thieno-[2, a 3-b] thiophene among X and the X '.

16, the compound represented of following formula:

Wherein

N is the integer of 2-50000, comprises end value,

Y is-CZ ¹=CZ ²-,-C=C-phenyl, naphthyl, pyrryl, thienyl, thieno-[3,4-b] thiophene, thieno-[2,3-b] thiophene and

Z ¹And Z ²Be independently selected from H, F, Cl or CN.

17, the compound of claim 16, wherein n is the integer of 2-10, comprises end value.

18, the compound of claim 16, wherein n is 11-50,000 integer comprises end value.

19, the compound of claim 18, wherein Y is-CH=CH-.

20, the compound of claim 18, wherein Y is-C ≡ C-.

21, the compound of claim 18, wherein Y is selected from phenyl, naphthyl, pyrryl, thienyl, thieno-[3,4-b] thiophene, thieno-[2,3-b] thiophene.

22, a kind of thing composition, it is by the compound of the claim of handling with doping agent 21.

23, the material composition of claim 22, wherein doping agent is a p-type doping agent.

24, the material composition of claim 22, wherein doping agent is a n-type doping agent.

25, a kind of material composition, it is the compound that is dispersed in the claim 21 in the fluid.

26, the material composition of claim 25, wherein fluid comprises water.

27, the material composition of claim 25, wherein fluid is a water.

28, the compound represented of following formula:

Wherein R is perfluorination primary, the second month in a season, the tertiary alkyl with 1-8 carbon atom, and n is 2-50, and 000 integer comprises end value.

29, the compound of claim 28, wherein R three fluoridizes methyl, perfluor ethyl, perfluoro propyl, perfluoro butyl, 2,2,2-trifluoromethyl-ethyl or 2,2,2-three fluoro-1,1-di-trifluoromethyl-ethyl.

30, the compound of claim 28, wherein R is a perfluoro butyl.

31, a kind of material composition, it is by the compound of the claim of handling with doping agent 28.

32, the material composition of claim 31, wherein doping agent is a p-type doping agent.

33, the material composition of claim 31, wherein doping agent is a n-type doping agent.

34, the material composition of claim 32, it is dispersed in the fluid, and described fluid is selected from polyacrylic acid, polymethyl acrylic acid, polymaleic acid, polystyrolsulfon acid, perfluorinated sulfonic acid polymer, polyvinylsulfonic acid and poly-(vinylbenzene-copolymerization-vinyl cyanide) sulfonic acid and their mixture.