CN106032401B - A kind of organic polymer, its preparation method and application - Google Patents
A kind of organic polymer, its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of new organic polymer, its preparation method and application.The halide derivative that the new organic polymer can be obtained by the chromene for first condensing double thiophene and chromene halogenation, react and prepare under metallic catalyst with the monomer containing aromatic group again, aromatic group is connected with the chromene and chromene unit of double thiophene fusions by conjugated manner.The new organic polymer of the present invention has good environment stability and photoelectric properties, also there is good solution processability energy at the same time, synthesis is flexible, it is easy to follow-up moditied processing, can the extensive use in classes of semiconductors electronics, the photoelectric devices such as organic light emitting diode, Organic Thin Film Transistors and organic optical sensor.
Description
Technical field
The invention belongs to organic photoelectrical material technical field, and in particular to a kind of conjugated polymer organic semiconducting materials,
Its preparation method and its application in organic photoelectric technical field.
Background technology
In recent years, the field that organic print electronic field is emerging as one, is still evolving, obtains in the nearly more than ten years
To extensive concern and develop rapidly.Organic electronic material with species due to enriching, raw material is cheap, can pass through chemical composition
The solvable liquefaction processing of the features such as modification adjusts molecule performance, product is light, thin, flexible, particularly material and printable method, are realized
Volume to volume large area, the low cost of electronic device are manufactured and paid close attention to by industrial circle.Printed electronic device is printed since it is simple
Brush manufacture craft and the non-selectivity to base material, make it in large area, flexibility, inexpensive electronic device application field,
There is the incomparable advantage of silicon-based semiconductor microelectronic component.
However, to prepare organic electronic device using a variety of printing technologies, the technology such as template/silk-screen printing,
Flexible version printing, intaglio printing, hectographic printing, ink jet printing and micro-contact printing etc..So this semi-conducting material is meeting
While high mobility itself and good solution processability, moreover it is possible to which there is higher environmental stability (light, heat, oxygen etc.).In this way,
It will likely become the ideal material of printed electronic industry.
Polymer semiconducting material is due to good dissolubility and processing performance, and is very suitable for printed electronic row
The candidate material that industry uses.Such as the polythiophene class material being widely studied, by adjusting the structural regularity of homopolymer, altogether
The electron energy level of polymers can realize 0.1~0.4cm with space structure and the means such as arrangement2The mobility of/Vs, can be very good
Meet requirement of the printed electronic field to material solution processability and mobility.But film crystalline substance is being made in current polymer-based material
Usually more sensitive to environmental factors such as water oxygens during body pipe, manufacture craft and stability to device have considerable influence, this will
Its industrial applications is limited significantly with promoting.The high new function material of environmental stability is thus designed and developed with particularly significant
Practical value.
The content of the invention
It is an object of the present invention to providing a kind of organic polymer material with high environmental stability, so as to overcome
Deficiency of the prior art.
Organic polymer provided by the invention, it has following structural formula：
Wherein, Ar is aromatic group；R、R1And R2For the unit being connected with main body framework, separately selected from hydrogen atom
Or alkenyl of the alkyl chain with 2~40 carbon atoms, alkynyl, aryl, aryl alkyl are either with 2~40 carbon
Atom, but wherein more than 1 carbon atom by hetero atom or substitution functional group substitute alkenyl, alkynyl, aryl either have 2~
40 carbon atoms, but alkenyl, the alkynes that the hydrogen atom wherein on more than 1 carbon atom is substituted by halogen atom or substitution functional group
Base, aryl；Wherein, the hetero atom includes Si, Se, O, S or N；The substitution functional group includes alkenyl, alkynyl, aryl, hydroxyl
Base, amino, carbonyl, carboxyl, ester group, cyano group or nitro；N is the degree of polymerization of the organic polymer, its numerical value is greater than or waits
In 4 natural number.
Wherein, the aromatic group Ar is selected from fluorenes, silicon fluorene, carbazole, benzene, thiophene, bithiophene, benzene thiophene, thieno
One kind in one kind in cyclopentadiene, diazosulfide and pyrrolo-pyrrole-dione, or above group derivative.
Further, the structure of the aromatic group Ar is such as one kind in lower structure：
Wherein R0、R3、R4、R5And R6Either separately there are 2~40 carbon originals selected from hydrogen atom or alkyl chain
Alkenyl, alkynyl, aryl, the aryl alkyl of son either have 2~40 carbon atoms, but wherein more than 1 carbon atom is by miscellaneous original
Son or alkenyl, alkynyl, the aryl of the substitution of substitution functional group either have 2~40 carbon atoms, but wherein more than 1 carbon atom
On hydrogen atom by halogen atom or substitution the functional group alkenyl, alkynyl, the aryl that substitute；- * passes through coupling reaction for monomer
Join domain；Wherein, the hetero atom includes Si, Se, O, S or N；The substitution functional group includes alkenyl, alkynyl, aryl, hydroxyl
Base, amino, carbonyl, carboxyl, ester group, cyano group or nitro.
Further, which prepared and formed by coupling reaction by monomer monomer I and monomer II；
Wherein, monomer I is：M-Ar-M, M are zinc halide, magnesium halide, SnMe3、SnBu3、B(OH)2Or haveCycliborate；Monomer II is：X is halogen atom.
Wherein, the alkyl chain includes：
Straight chain, side chain or cyclic alkyl chain with 1~22 carbon atom；
With 1~22 carbon atom, but wherein more than 1 carbon atom by hetero atom or substitution functional group substitute straight chain,
Side chain or cyclic alkyl chain；
With 1~22 carbon atom, but the hydrogen atom wherein on more than 1 carbon atom is by halogen atom or substitution functional group
Substituted straight chain, side chain or cyclic alkyl chain；
The hetero atom includes Si, Se, O, S or N；
The substitution functional group includes alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro.
Another object of the present invention is to provide a kind of method for preparing aforementioned organic polymer, it is simple with technique,
The advantages that flexibly controllable.
This method includes：The chromene that first double thiophene are condensed and chromene halogenation, obtain its halide derivative；Again
The halide derivative and the monomer containing aromatic group Ar are subjected to coupling reaction under metallic catalyst, make aromatic group Ar with
The chromene and chromene unit of double thiophene fusions are connected by conjugated manner, obtain the organic polymer.
Wherein, the coupling reaction is Suzuki couplings, Stille is coupled, Negishi is coupled, Hiyama is coupled or C-H
Activate direct coupling reaction.
Further, the synthetic route of this method includes：
Wherein, M is zinc halide, magnesium halide, SnMe3、SnBu3、B(OH)2Or haveCycliborate.
It is still another object of the present invention to provide the application of aforementioned organic polymer.The organic polymer has available for preparation
Machine semi-conducting material, layer or component, applied in semi-conductor electronic device and photoelectric device.The semi-conductor electronic device and light
Electrical part includes organic electroluminescence device, organic field effect tube, Organic Thin Film Transistors, organic light-emitting transistor, has
Machine integrated circuit, organic solar batteries, organic field quenching device, light-emitting electrochemical cell, organic laser diode or organic
Photoreceptor.
Compared with prior art, the present invention at least has the following advantages that：
(1) good environmental stability and photo electric are made it have because introducing oxygen bridge in organic polymer of the invention
Can, while the presence of oxygen atom and sulphur atom, a variety of interactions can be formed, there is more preferable pi-pi accumulation effect, be conducive to
The transmission of electric charge, can be applied to high mobility electronic devices, obtain better performance.
(2) in organic polymer of the invention by introducing solubilizing group, it may also reach up the flat of dissolubility and flatness
Weighing apparatus, has good solution processability energy, is conducive to the preparation of later printable electronics.
(3) organic polymer semiconductor materials synthesis route of the invention is flexible, and it is big can to modify space.
(4) organic semiconducting materials of the invention can be widely used in organic electroluminescence device (OLED, PLED), have
Field effect transistors (OFET), Organic Thin Film Transistors (OTFT), organic light-emitting transistor (OLET), organic integrated circuits
(OIC), organic solar batteries (OSC), organic field quenching device (OFQD), light-emitting electrochemical cell (LEC), organic laser two
Pole pipe (O-Laser) or organophotoreceptorswith etc..
Brief description of the drawings
Fig. 1 is the process flow chart of the preparation method of organic polymer provided by the invention.
Fig. 2 is the structure diagram of film transistor device in a preferred embodiment of the present invention.
Embodiment
Describe the exemplary embodiment of the present invention in detail below with reference to accompanying drawings.
Carry out detailed description of the present invention exemplary embodiment below with reference to attached drawing, however, attached drawing simply schematically shows
Go out the specific example of the present invention, and do not have restriction effect.However, it will be understood by those skilled in the art that do not departing from
In the case of the protection domain that the claim of the present invention is limited, various modifications and deformation can be carried out to it.
First, it is an object of the present invention to provide a kind of organic polymer material with high environmental stability.Should
Organic polymer is connected by conjugated manner and is formed with the chromene and chromene unit of double thiophene fusions by aromatic group,
It has following structural formula：
Wherein, Ar is aromatic group；R、R1And R2For the unit being connected with main body framework, separately selected from hydrogen atom
Or alkyl chain；N is the degree of polymerization of the organic polymer, its numerical value is greater than or equal to 4 natural number.
Because introducing oxygen bridge in the organic polymer, good environmental stability and photoelectric properties, while oxygen are made it have
The presence of atom and sulphur atom, can form a variety of interactions, have more preferable pi-pi accumulation effect, be conducive to the biography of electric charge
It is defeated, high mobility electronic devices are can be applied to, obtain better performance.
Wherein, aromatic group Ar can be fluorenes, silicon fluorene, carbazole, benzene, thiophene, bithiophene, benzene thiophene, thieno ring
One kind in pentadiene, diazosulfide and pyrrolo-pyrrole-dione, or more one kind in all group derivatives.
Further, in order to help to understand Ar implications, several frequently seen Ar monomers are set forth below, without should be office of the present invention
It is limited to following several monomers, the R in structure is set forth below0、R3、R4、R5And R6Separately it is selected from hydrogen atom or alkyl
Chain ,-* are join domain of the monomer by coupling reaction.
The structure of foregoing common monomer is as follows：
The effect of Ar groups is：Dissolubility and the chemical reaction of the polymer can be changed using different Ar groups
Property, by the way that more complicated sulfur family hetero atom fused ring polymer to further being modified on derivative Ar groups, can be prepared, reach molten
The balance of solution property and flatness, has good solution processability energy, is conducive to the preparation of later printable electronics.
Alkyl chain mentioned above includes：Straight chain, side chain or cyclic alkyl chain with 1~22 carbon atom；With 1
~22 carbon atoms, but straight chain, side chain or the ring-type alkane that wherein more than 1 carbon atom is substituted by hetero atom or substitution functional group
Base chain；With 1~22 carbon atom, but the hydrogen atom wherein on more than 1 carbon atom is taken by halogen atom or substitution functional group
Straight chain, side chain or the cyclic alkyl chain in generation.Further, above-described R, R1And R2And R0、R3、R4、R5And R6May be used also
To be separately selected from the alkenyl with 2~40 carbon atoms, alkynyl, aryl, aryl alkyl either with 2~40 carbon
Atom, but wherein more than 1 carbon atom by hetero atom or substitution functional group substitute alkenyl, alkynyl, aryl either have 2~
40 carbon atoms, but alkenyl, the alkynes that the hydrogen atom wherein on more than 1 carbon atom is substituted by halogen atom or substitution functional group
Base, aryl.Wherein, the hetero atom includes Si, Se, O, S or N；The substitution functional group includes alkenyl, alkynyl, aryl, hydroxyl
Base, amino, carbonyl, carboxyl, ester group, cyano group or nitro.
Another object of the present invention is to provide a kind of method for preparing aforementioned organic polymer, it is simple with technique,
The advantages that flexibly controllable.
As shown in Figure 1, the preparation method of aforementioned organic polymer includes：S10, the chromene acene for condensing double thiophene
And pyrans halogenation, obtain its halide derivative；S20, urge the halide derivative and the monomer containing aromatic group Ar in metal
Coupling reaction is carried out under agent, obtains the organic polymer.Wherein, aromatic group Ar and double thiophene are thick after progress coupling reaction
The chromene and chromene unit of conjunction are connected by conjugated manner.
Wherein, the synthesis of the chromene and chromene of double thiophene fusions may be referred to Chinese patent publication
CN103497758A, the entire disclosure are included herein with references manner.Foregoing coupling reaction includes but not limited to
Suzuki couplings, Stille couplings, Negishi couplings, Hiyama couplings, C-H activation directly coupling etc..
As one of scheme that can implement, this method includes but not limited to following route：First to the benzo of thiophene fusion
Pyrans and chromene carry out bromination and alkylation is modified, and obtain a brominated monomer (monomer II), then again with aromatic group
Rate of charge of the Ar monomers (monomer I) by the cross-coupling reaction that Pd is catalyzed according to equivalent, in organic solvent reaction obtain
Foregoing subject polymer.Wherein, suitable brominated reagent includes bromine and N-bromosuccinimide.Further, this method
Synthetic route can by it is following reaction illustrate：
Wherein, in monomer I, M is zinc halide, magnesium halide, SnMe3、SnBu3、B(OH)2Or haveRing-type
Borate；Br atoms in monomer II can also use other halogen atoms to replace.
It is described further below in conjunction with some preferred embodiments：
Embodiment 1
Main two parts of preparation and polymerisation for including monomer of preparation of organic polymer provided in this embodiment.It is first
First, the synthesis of the chromene and chromene of double thiophene fusions may be referred to Chinese patent publication N0.103497758A
Prepare, 2,7- double (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl)-N-9- heptadecyl carbazoles are according to document
It is prepared by (N.Blouin, A.Michaud, M.Leclerc, Adv.Mater., 2007,19,2295-2300).
Specifically, monomer 1 (chromenes and chromene of double thiophene fusions) and polymer P1The conjunction of (target product)
It is as follows into route：
First, the synthesis of monomer 1：
Specifically reaction condition is：(I)Br2, CS2, reflux, 24h.(Ⅱ)CH3COOH, Zn, reflux, 2h.(Ⅲ)
C8H17MgBr, [NiCl2(dppp)], Et2O, reflux, 12h.(Ⅳ)Br2, CH2Cl2, rt, 2h.
More specifically：
Step (I)：To the chromene and the carbon disulfide solution of chromene condensed containing 0.96g (3mmol) thiophene
Carbon disulfide (20mL) solution containing 9.6g bromines is added dropwise in (40mL), then mixed liquor is heated slowly to flow back and protects
Hold 24 it is small when, after reaction, saturation sodium hydrogensulfite is added into reaction solution, filtering, obtained solid uses water and ethanol respectively
Washing is three times, dry, which has poor dissolubility, is not further purified and directly carries out next step reaction.
Step (II)：The compound 0.636g (1mmol) that the thiophene that the tetrabromo obtained in step (I) substitutes condenses is dissolved in
Then be heated to flow back in 100mL acetic acid, zinc powder 0.143g (2.2mmol) be added portionwise, continue reflux 4 it is small when, reaction terminates
Postcooling is diluted with water to room temperature, filters out precipitation, be washed with water, drying, faint yellow solid is obtained with THF- recrystallizing methanols.
Step (III):First prepare Grignard Reagent n-Oct-MgBr：In 25mL two-mouth bottles add magnesium rod (0.14g,
5.8mmol), very small amount iodine grain, in N2Protection is lower to add 10mL ether, low-grade fever, be slowly added dropwise 1- n-octane bromides (0.87mL,
5mmol, 99%) slightly boiling is maintained, when slowly reflux 1 is small after being added dropwise, obtain Grignard Reagent.Added in 100mL two-mouth bottles
The dibromo compound (0.478g, 1mmol) of gained, PdCl in step (II)2(dppf) (36.8mg, 0.05mmol), ether
(50mL), the Grignard Reagent made is slowly added dropwise at 0 DEG C, when system reflux 12 is small after be cooled to room temperature, add 20mL saturations NH4Cl
Reaction is quenched in aqueous solution, and organic matter is extracted with ether, and organic phase merges, saturated salt solution and deionized water washing, solution pass through
Anhydrous Na2SO4Filtered after drying, screw out solvent, the isolated alkylated thiophene condensed compounds of crude by column chromatography.
Step (IV):At room temperature, bromine (0.14mL, 2.7mmol) is used into 5mLCH2Cl2Dilution, is slowly dropped into step (III)
The CH of middle gained compound (0.545g, 1mmol)2Cl2In (30mL) solution, reaction 2 it is small when after use saturation Na2SO3Aqueous solution is quenched
The Br of sterilized amount2, organic layer is isolated, is washed with saturated salt solution, deionized water, solution is through anhydrous MgSO4Filtered after drying,
Solvent is screwed out, column chromatography obtains monomer 1.
2nd, polymer P1Synthesis：
By double (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-the diyl)-N-9- 17 of 131mg (0.2mmo1) 2,7-
Alkyl carbazole, 140mg (0.2mmol) monomer 1,3mgPd2(dba)3, the P (o-tol) of 6mg3Add in the two-mouth bottle of 25m1, take out
Ventilation is full of to hydrogen three times, and 1.6m120%Et is added with syringe4NOHI organic alkali solutions and 10mL toluene, back flow reaction
48 it is small when, be separately added into phenyl boric acid and bromobenzene end-blocking, will reaction solution instill methanol in separate out polymer, then by polymer in rope
Washed in family name's extractor, finally polymer is being dried in vacuum drying oven, is finally obtaining 120mg polymer Ps1, yield：
64%.
Embodiment 2
The synthetic route of organic polymer in the present embodiment is as follows：
First, the synthesis of monomer 1 is the same as embodiment 1, another monomer 2,7- double (4,4,5,5- tetramethyls -1,3,2- dioxa boron
Alkane-diyl)-docosyl fluorenes directly buy gained.
2nd, polymer P2Synthesis：
By double (4,4,5,5- tetramethyls -1,3,2- dioxaborinates-diyl) -- the dioctyls of 377mg (0.5mmo1) 2,7-
Fluorenes, 350mg (0.5mmol) monomer 1,6mgPd2(dba)3, the P (o-tol) of 12mg3Add in the two-mouth bottle of 25m1, substitute gas three
It is secondary to be full of to hydrogen, add 4m120%Et with syringe4NOHI organic alkali solutions and 10mL toluene, when back flow reaction 72 is small, point
Not Jia Ru phenyl boric acid and bromobenzene end-blocking, will reaction solution instill methanol in separate out polymer, then by polymer in apparatus,Soxhlet's
Middle washing, is finally drying polymer in vacuum drying oven, finally obtains 245mg black polymers P2, yield：47%.
Embodiment 3
The synthetic route of organic polymer in the present embodiment is as follows：
Polymer P3Synthetic method it is identical with the method in embodiment 1,2, two kinds of monomeric charges are 0.2mmol than respectively,
Remaining also with example 1,2, obtain 81mg black solid polymer Ps3, yield：60%.
Embodiment 4
The preparation of semiconductor devices based on the chromene condensed containing thiophene and the polymer of benzopyran structure unit.
As it was previously stated, the organic polymer of the present invention can be used for preparing organic semiconducting materials, layer or component, applied to half
In conducting electrons device and photoelectric device.The semi-conductor electronic device and photoelectric device include organic electroluminescence device, have
It is field effect transistors, Organic Thin Film Transistors, organic light-emitting transistor, organic integrated circuits, organic solar batteries, organic
Field quenching device, light-emitting electrochemical cell, organic laser diode or organophotoreceptorswith.
The chromene of the fusion containing thiophene involved in the present embodiment and the semiconductor of the polymer of benzopyran structure unit
Device (specifically, field-effect transistor, FET) should include grid, gate insulation layer, source/drain, and channel formation region,
Wherein described grid, gate insulation layer, source/drain and channel formation region are arranged on matrix, channel formation region by containing
The chromene of thiophene fusion and the polymer composition of benzopyran structure unit.
More specifically, as shown in Fig. 2, by taking bottom gate/top contact transistor npn npn as an example, which includes：It is formed in
Gate electrode J3 on substrate A1, A2；Form the gate insulator D1 on gate electrode J3；The raceway groove being formed on gate insulator D1
Form area S1 and channel formation region extension S2；Source/drain electrode J1, J2 being formed on the extension S2 of channel formation region.
Aforementioned substrates include the substrate that is made of silicon substrate and set in its surface be made of silica it is exhausted
Edge layer.Grid is the silicon of heavy doping, and source/drain is the gold composition that patterning plates, and forms channel shape.Passage is formed
Region and channel formation region extension are by the chromene described in the present invention condensed containing thiophene and chromene knot
The compound of one kind in the polymer of structure unit or itself and other materials composition is formed.
The above is only the embodiment of the application, it is noted that for the ordinary skill people of the art
For member, on the premise of the application principle is not departed from, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as the protection domain of the application.
Claims (10)
1. a kind of organic polymer, it is characterised in that it has following structural formula：
Wherein, Ar is aromatic group；R、R1And R2Separately selected from hydrogen atom or alkyl chain either with 2~40
Alkenyl, alkynyl, aryl, the aryl alkyl of carbon atom either have 2~40 carbon atoms, but wherein more than 1 carbon atom quilt
Hetero atom or alkenyl, alkynyl, the aryl of the substitution of substitution functional group either have 2~40 carbon atoms, but wherein more than 1 carbon
Alkenyl, alkynyl, the aryl that hydrogen atom on atom is substituted by halogen atom or substitution functional group；
Wherein, the hetero atom includes Si, Se, O, S or N；The substitution functional group includes alkenyl, alkynyl, aryl, hydroxyl, ammonia
Base, carbonyl, carboxyl, ester group, cyano group or nitro；
Wherein, n is the natural number more than or equal to 4.
2. organic polymer according to claim 1, it is characterised in that the aromatic group Ar is selected from fluorenes, silicon fluorene, click
One in azoles, benzene, thiophene, bithiophene, benzene thiophene, thiophene pentalene, diazosulfide and pyrrolo-pyrrole-dione
Kind, or one kind in above group derivative.
3. organic polymer according to claim 1, it is characterised in that the structure of the aromatic group Ar is such as lower structure
In one kind：
Wherein R0、R3、R4、R5And R6Separately selected from hydrogen atom or alkyl chain either with 2~40 carbon atoms
Alkenyl, alkynyl, aryl, aryl alkyl either have 2~40 carbon atoms, but wherein more than 1 carbon atom by hetero atom or
Alkenyl, alkynyl, the aryl of substitution functional group substitution either have 2~40 carbon atoms, but wherein on more than 1 carbon atom
Alkenyl, alkynyl, the aryl that hydrogen atom is substituted by halogen atom or substitution functional group；- * is connection of the monomer by coupling reaction
Region；
Wherein, the hetero atom includes Si, Se, O, S or N；The substitution functional group includes alkenyl, alkynyl, aryl, hydroxyl, ammonia
Base, carbonyl, carboxyl, ester group, cyano group or nitro.
4. organic polymer according to claim 3, it is characterised in that the polymer is by monomer monomer I and monomer II
Prepare to be formed by coupling reaction；
Wherein, monomer I is：M-Ar-M, M are zinc halide, magnesium halide, SnMe3、SnBu3、B(OH)2Or have's
Cycliborate；Monomer II is：X is halogen atom.
5. according to any organic polymers of claim 1-4, it is characterised in that the alkyl chain includes：
Straight chain, side chain or cyclic alkyl chain with 1~22 carbon atom；
With 1~22 carbon atom, but straight chain, the side chain that wherein more than 1 carbon atom is substituted by hetero atom or substitution functional group
Or cyclic alkyl chain；
With 1~22 carbon atom, but the hydrogen atom wherein on more than 1 carbon atom is substituted by halogen atom or substitution functional group
Straight chain, side chain or cyclic alkyl chain；
The hetero atom includes Si, Se, O, S or N；
The substitution functional group includes alkenyl, alkynyl, aryl, hydroxyl, amino, carbonyl, carboxyl, ester group, cyano group or nitro.
6. the preparation method of any organic polymers of claim 1-5, it is characterised in that the benzene for first condensing double thiophene
And pyrans and chromene halogenation, obtain its halide derivative；Again by the halide derivative and the monomer containing aromatic group Ar
Coupling reaction is carried out under metallic catalyst, the chromene and chromene unit for making aromatic group Ar and double thiophene fusions lead to
Conjugated manner connection is crossed, obtains the organic polymer.
7. preparation method according to claim 6, it is characterised in that the coupling reaction is Suzuki couplings, Stille
Coupling, Negishi couplings, Hiyama couplings or C-H activate direct coupling reaction.
8. the preparation method according to claim 6 or 7, it is characterised in that the synthetic route of this method includes：
Wherein, M is zinc halide, magnesium halide, SnMe3、SnBu3、B(OH)2Or haveCycliborate.
9. a kind of organic semiconducting materials, layer or component, it is characterised in that comprising organic as described in claim 1-5 is any
Polymer.
10. application of any organic polymers of claim 1-5 in semi-conductor electronic device and photoelectric device；It is described
Semi-conductor electronic device and photoelectric device include organic electroluminescence device, organic field effect tube, Organic Thin Film Transistors,
It is organic light-emitting transistor, organic integrated circuits, organic solar batteries, organic field quenching device, light-emitting electrochemical cell, organic
Laser diode or organophotoreceptorswith.
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| CN102675332A (en) * | 2011-03-08 | 2012-09-19 | 施乐公司 | Small molecule semiconductor and semiconductor composition and electronic device comprising the same |
| CN103497758A (en) * | 2013-08-06 | 2014-01-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel organic semiconductor material, preparation method, and applications thereof |
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| CN102675332A (en) * | 2011-03-08 | 2012-09-19 | 施乐公司 | Small molecule semiconductor and semiconductor composition and electronic device comprising the same |
| CN103497758A (en) * | 2013-08-06 | 2014-01-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel organic semiconductor material, preparation method, and applications thereof |
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| CN106032401A (en) | 2016-10-19 |
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