CN102250323B - Copolymers containing fluorene, anthracene and diazosulfide units, preparation method thereof, and application thereof - Google Patents
Copolymers containing fluorene, anthracene and diazosulfide units, preparation method thereof, and application thereof Download PDFInfo
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- CN102250323B CN102250323B CN 201010180355 CN201010180355A CN102250323B CN 102250323 B CN102250323 B CN 102250323B CN 201010180355 CN201010180355 CN 201010180355 CN 201010180355 A CN201010180355 A CN 201010180355A CN 102250323 B CN102250323 B CN 102250323B
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- 0 CC1C(C)(*)C(C)C(C)(C)C1 Chemical compound CC1C(C)(*)C(C)C(C)(C)C1 0.000 description 4
- OOYQYJLQEIREKC-UHFFFAOYSA-N BrC(C1=CCCC=C11)=C(C=CC=C2)C2=C1Br Chemical compound BrC(C1=CCCC=C11)=C(C=CC=C2)C2=C1Br OOYQYJLQEIREKC-UHFFFAOYSA-N 0.000 description 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N Brc(c1n[s]nc11)ccc1Br Chemical compound Brc(c1n[s]nc11)ccc1Br FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses copolymers containing fluorene, anthracene and diazosulfide units, a preparation method of the copolymers, and an application of the copolymers. The copolymers are represented by a molecular general formula (I). In the formula, n is a natural number from 1 to 500. m is a natural number, wherein 1<=m<=20. x, y are positive real numbers, and x+y=1. R1 and R2 are selected from hydrogen atom, halogen, cyan, optionally substituted or non-substituted C1 to C40 alkyl, aryl or heteroaryl. R3 is selected from hydrogen atom, cyan, optionally substituted or non-substituted C1 to C40 alkyl, C1 to C40 alkoxy, C6 to C40 aryl, C6 to C40 aralkyl, or C6 to C40 aryl alkoxy. The copolymers containing anthracene and diazosulfide units have high solubility, high carrier mobility, high light absorbance, wide light absorbing scope, and improved utilance of sunlight. The preparation method of the copolymers is easy; the yield is high; and the processes are easy to operate and to control.
Description
Technical field
The invention belongs to the organic compound synthesis technical field, relate to specifically a kind of fluorenes, anthracene and diazosulfide unit multipolymer and its preparation method and application of containing.
Background technology
Current world economy mainly is to be based upon with fossil energy, such as the economy on the bases such as coal, oil and natural gas.Yet these non-renewable fossil energies are all in continuous exhaustion.Entered since 21 century, the problems such as global energy problem and consequent environmental pollution and climate warming show especially and gradually aggravation day by day.Because sun power has and distributes generally and wide, resource quantity is many, and is pollution-free, cleaning, and safety and obtain the outstanding advantages such as convenient is considered to one of most promising renewable energy source.Solar cell directly changes into electric energy to solar energy, is to utilize the practicable effective ways of sun power.Yet present commercial solar cell also is confined to the inorganic solar cell such as silica-based, but their price is too expensive, has exceeded the general acceptable degree of present people, and this has limited their use range greatly.In order to reduce the battery cost, expand range of application, for a long time, people are seeking novel solar cell material always.
Organic solar batteries is a kind of novel solar cell, limited with respect to the inorganic semiconductor material source, expensive, poisonous, complicated process of preparation, cost is too high, and it has some incomparable advantages of inorganic solar cell, and is extensive such as material source, structure diversity and Modulatory character, with low cost, safety and environmental protection, manufacture craft is simple, product weight is light, but large area flexible preparation etc. can be widely used in the multiple fields such as building, illumination and generating, has important development and application prospect.Therefore, the research institution of lot of domestic and foreign and enterprise etc. have all given suitable concern and input.Yet up to the present, the photoelectric transformation efficiency of organic solar batteries is than inorganic solar cell or much lower.Therefore, the organic semiconductor material of development of new is significant for the efficient that improves organic solar batteries.
Summary of the invention
The object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of fluorenes, anthracene and diazosulfide unit multipolymer of containing is provided, this multipolymer has good photo and thermal stability and film-forming properties, have lower energy gap, higher mobility, absorption region to spectrum is wide, Effective Raise current carrier in active layer material internal delivery efficient.
Another object of the present invention is to provide the preparation method who contains fluorenes, anthracene and diazosulfide unit multipolymer that a kind of technique is simple, productive rate is high, be easy to operate and control.
Further aim of the present invention be to provide above-mentioned contain fluorenes, anthracene and diazosulfide unit multipolymer at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and the application in the organic laser apparatus.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of fluorenes, anthracene and diazosulfide unit multipolymer of containing, its general formula of molecular structure is following (I):
In the formula, n is the polymerization degree, and is 1～500 natural number; M is natural number, and 1≤m≤20; X, y are real positive value, and x+y=1; R
1, R
2Be selected from hydrogen atom, halogen, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted aryl, perhaps optional the replacement or unsubstituted heteroaryl; R
3Be selected from hydrogen atom, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted C
1～C
40Alkoxyl group, the optional replacement or unsubstituted C
6～C
40Aryl, the optional replacement or unsubstituted C
6～C
40Aralkyl, perhaps optional the replacement or unsubstituted C
6～C
40Alkoxy aryl.
And a kind of fluorenes, anthracene and diazosulfide unit multipolymer preparation method of containing comprises the steps:
The compd A, B, the C that provide respectively following structural formula to represent,
Wherein, m is natural number, and 1≤m≤20; R
1, R
2Be selected from hydrogen atom, halogen, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted aryl or optional the replacement or unsubstituted heteroaryl; R
3Be selected from hydrogen atom, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted C
1～C
40Alkoxyl group, the optional replacement or unsubstituted C
6～C
40Aryl, the optional replacement or unsubstituted C
6～C
40Aralkyl, the optional replacement or unsubstituted C
6～C
40Alkoxy aryl;
In the system of anhydrous, oxygen-free environment and organic solvent, with alkyl derivative and the 2-isopropoxy-4,4 of compd A, lithium, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes react, and generate compound 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes;
In anaerobic and alkaline environment and under the condition of catalyzer and organic solvent existence, with compound 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes, compd B and Compound C are carried out the Suzuki reaction, obtain following general structure and be that I represents contains fluorenes, anthracene and diazosulfide unit multipolymer
In the formula, x, y are real positive value, and x+y=1; N is the polymerization degree, and value is 1～500 natural number.
Further, provided by the invention contain fluorenes, anthracene and diazosulfide unit multipolymer at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and the application in the organic laser apparatus.
Technique scheme compared with prior art possesses following advantage:
1. the existence of the fluorenes unit of easily modifying has good photo and thermal stability and film-forming properties so that contain fluorenes, anthracene and diazosulfide unit multipolymer;
2. the existence of anthracene unit, have good stability and film-forming properties preferably so that contain fluorenes, anthracene and diazosulfide unit multipolymer, and so that presenting wider finger peak, the ultraviolet-visible spectrum of this multipolymer absorbs, thereby improved it to sun Optical Absorption coverage, strengthened it to carrier transmission characteristics;
3. the diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the metallic cathodes such as magnesium, aluminium, has preferably electric transmission character, can also regulate simultaneously the energy gap of material, thereby has lower energy gap so that contain fluorenes, anthracene and diazosulfide unit polymkeric substance, higher carrier mobility, the absorption region of spectrum is wide, and effectively raises current carrier in active layer material internal delivery efficient;
4. this multipolymer preparation method technique is simple, and productive rate is high, and reaction conditions is gentle, is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the synoptic diagram that contains fluorenes, anthracene and diazosulfide unit copolymer molecule general structure of the embodiment of the invention;
Fig. 2 is that contain fluorenes, anthracene and the diazosulfide unit multipolymer that adopt the embodiment of the invention 1 to prepare are the structural representation of the organic solar batteries device of active coating;
Fig. 3 be adopt the embodiment of the invention 1 preparation to contain fluorenes, anthracene and diazosulfide unit multipolymer be the structural representation of the organic electroluminescence device of luminescent layer;
Fig. 4 is that contain fluorenes, anthracene and the diazosulfide unit multipolymer that adopt the embodiment of the invention 1 to prepare are the structural representation of the organic field effect tube device of organic semiconductor layer.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
See also Fig. 1, what show the embodiment of the invention contains fluorenes, anthracene and diazosulfide unit multipolymer, and its general formula of molecular structure is following (I):
In the formula, n is the polymerization degree, and is 1～500 natural number; M is natural number, and 1≤m≤20; X, y are real positive value, and x+y=1; R
1, R
2Be selected from hydrogen atom, halogen, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted aryl, perhaps optional the replacement or unsubstituted heteroaryl; R
3Be selected from hydrogen atom, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted C
1～C
40Alkoxyl group, the optional replacement or unsubstituted C
6～C
40Aryl, the optional replacement or unsubstituted C
6～C
40Aralkyl, perhaps optional the replacement or unsubstituted C
6～C
40Alkoxy aryl.Wherein, R
1, R
2The position of substitution optional position that can on corresponding phenyl ring, can replace.
Above-mentioned R
1, R
2Be preferably optional the replacement or unsubstituted C
1～C
40Alkyl; R
3Be preferably optional the replacement or unsubstituted C
1～C
40Alkoxyl group.This be because, suitably long such as C
8～C
12Alkyl or alkoxyl group can improve photo and thermal stability and the film-forming properties of present embodiment multipolymer, effectively reduce the energy gap of this multipolymer, the electronic mobility of raising.
Above-mentionedly contain the existence that fluorenes, anthracene and diazosulfide unit multipolymer contain the fluorenes unit of easy modification, so that this multipolymer has good photo and thermal stability and film-forming properties; The anthracene unit that contains has good stability and film-forming properties preferably so that contain fluorenes, anthracene and diazosulfide unit multipolymer, and so that presenting wider finger peak, the ultraviolet-visible spectrum of this multipolymer absorbs, thereby improved it to sun Optical Absorption coverage, strengthened it to carrier transmission characteristics, hole mobility can reach 3cm under its crystal room temperature
2/ Vs; The diazosulfide unit that contains has excellent reduction reversibility, very approaching with the work content value of the metallic cathodes such as magnesium, aluminium, has preferably electric transmission character, can also regulate simultaneously the energy gap of material, thereby has lower energy gap so that contain fluorenes, anthracene and diazosulfide unit polymkeric substance, higher carrier mobility, the absorption region of spectrum is wide, and effectively raises current carrier in active layer material internal delivery efficient.With the multipolymer of the present embodiment polymer solar battery as the active material preparation, through behind the high temperature annealing, can effectively increase order and the regularity arranged between interior each group of molecule and molecule segment, improve transmission speed and the efficient of carrier mobility, and then improve photoelectric transformation efficiency.
And present embodiment also provides this to contain fluorenes, anthracene and diazosulfide unit multipolymer preparation method, comprises following steps:
1) compd A, B, the C that provide respectively following structural formula to represent,
Wherein, m is natural number, and 1≤m≤20; R
1, R
2Be selected from hydrogen atom, halogen, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted aryl or optional the replacement or unsubstituted heteroaryl; R
3Be selected from hydrogen atom, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted C
1～C
40Alkoxyl group, the optional replacement or unsubstituted C
6～C
40Aryl, the optional replacement or unsubstituted C
6～C
40Aralkyl, the optional replacement or unsubstituted C
6～C
40Alkoxy aryl;
2) in the system of anhydrous, oxygen-free environment and organic solvent, with alkyl derivative and the 2-isopropoxy-4,4 of compd A, lithium, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes react, and generate compound 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes, the chemical equation of this reactions steps is as follows:
3) in anaerobic and alkaline environment and under the condition of catalyzer and organic solvent existence, with compound 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes, compd B and Compound C are carried out the Suzuki reaction, obtain following general structure and be that I represents contains fluorenes, anthracene and diazosulfide unit multipolymer
In the formula, x, y are real positive value, and x+y=1; N is the polymerization degree, and value is 1～500 natural number; The chemical equation of Suzuki reaction is as follows:
In the above-mentioned steps (2), compound 2,7-two (4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane bases of 3,2-two)-9,9-dialkyl group fluorenes is the preparation method be preferably: in the system of anhydrous, oxygen-free environment and organic solvent, alkyl derivative with compd A and lithium reacts first, then add 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaboranes react and obtain described compound 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes product.
The alkyl derivative of compd A, lithium and 2-isopropoxy-4,4,5 described in the step (2), 5-tetramethyl--1,3, the mol ratio of assorted oxygen pentaborane (two tetramethyl ethylene ketones close two boron) three reactants of 2-two is preferably 1.0: 2.0～and 4.0: 2.0～4.0; Described organic solvent is preferably at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; The alkyl derivative of described lithium is that the alkyl derivative of lithium is at least a in n-Butyl Lithium, tert-butyl lithium, lithium methide, the phenyl lithium.The temperature of reaction of this step is preferably-70 ℃～-85 ℃, and the time is preferably 12～48 hours.
Above-mentioned steps (2) must be reacted in anhydrous and oxygen-free environment, and this is because there is water can cause the alkyl derivative of lithium, is decomposed such as butyllithium, so that should react unsuccessfully; Aerobic can cause 2-isopropoxy-4,4,5,5-tetramethyl--1,3, and 2-two assorted oxygen pentaboranes (two tetramethyl ethylene ketones close two boron) are oxidized, and reaction failure or productive rate are greatly reduced.Oxygen-free environment can adopt vacuum or be full of rare gas element and realize, preferably is full of rare gas element and realizes oxygen-free environment, and this rare gas element is the art rare gas element commonly used, such as nitrogen, argon gas etc., preferred nitrogen.
In the above-mentioned steps (3), catalyst loading is described compound 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,0.5%～15% of 9-dialkyl group fluorenes mole dosage, this catalyzer is preferably the mixture of organic palladium or organic palladium and organophosphorus ligand, and wherein, the organic palladium catalyzer is preferably Pd (PPh
3)
4, Pd
2(dba)
3Or Pd (PPh
3)
2Cl
2In at least a, organophosphorus ligand is preferred, but is not limited only to P (o-Tol)
3In the above-mentioned steps (3), in the presence that does not have alkali, the Suzuki reaction is to be difficult to occur, not even reaction.The power of alkali (negative ion) is not only depended in the impact of alkali in the reaction, and to take into account cationic character, if too little transition state ylide (Pd) intermediate that is unfavorable for generating the centre of positively charged ion, when speed and the efficient of the too little and conductively-closed of positively charged ion reaction will significantly descend, suitable large cationic alkali, can accelerate the speed of Suzuki reaction, therefore, alkali is preferably alkali metal hydroxide, alkaline carbonate, at least a in the tetraethyl ammonium hydroxide, its addition and described compound 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9, the mol ratio of 9-dialkyl group fluorenes is preferably 5～10: 1.
In the above-mentioned steps (3), compound 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9, the mol ratio of 9-dialkyl group fluorenes, compd B and Compound C three reactants is preferably m: p: q, wherein m=p+q, and m＞p＞0, m＞q＞0, at this moment, the ratio of m: p: q has determined the numerical value of x, y in the general formula (I), and the mathematical relation of m, p, q, x, y is m=p+q=n (x+y), wherein, n is the polymerization degree of general formula (I); Organic solvent is preferably one or more in toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; The temperature of this Suzuki reaction is preferably 60～95 ℃, and the reaction times is preferably 12～72 hours.Obtaining of compd B and C can obtain by the art technique means commonly used.
Above-mentioned steps (3) must be reacted in oxygen-free environment, and this is because the catalyzer of Suzuki reaction all is to be afraid of oxygen, if the existence of aerobic in the reaction system can cause catalyst deactivation, thereby causes the Suzuki reaction to carry out.Oxygen-free environment in the reaction system can adopt vacuum or be full of rare gas element and realize, preferably is full of rare gas element and realizes oxygen-free environment, and this rare gas element is the art rare gas element commonly used, such as nitrogen, argon gas etc., preferred nitrogen.
Contain among fluorenes, anthracene and the diazosulfide unit multipolymer preparation method at this, only need that reactant is pressed ratio and add, need not special equipment and environmental requirement, its preparation method technique is simple, and productive rate is high, and mild condition, be easy to operate and control, be suitable for suitability for industrialized production.
Because embodiment contains fluorenes, anthracene and diazosulfide unit multipolymer and has above-mentioned advantage, therefore, this contain fluorenes, anthracene and diazosulfide unit multipolymer can be at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and use in the organic laser apparatus.
Below illustrate the present invention by a plurality of embodiment and contain different structure of fluorenes, anthracene and diazosulfide unit multipolymer and preparation method thereof, with and the aspects such as application and performance.
Contain fluorenes, anthracene and diazosulfide unit multipolymer I
1Preparation, its structural formula is as follows:
In the formula, x=0.1; Y=0.9.
Its preparation comprises the steps:
1) 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene, its reaction is shown below:
The preparation detailed process is: put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Protection under, add 2 of white, 7-two bromo-9 in the there-necked flask, 9-dioctyl fluorene 9.0mmol injects the refining tetrahydrofuran solvent of 150ml with syringe, again under-70 ℃ of conditions, slowly inject the n-BuLi of 27.0mmol with syringe, after 2 hours, under-70 ℃ of conditions, inject the 2-isopropoxy-4 of 30.6mmol until stirring reaction with syringe, 4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes, then the temperature with reaction system rises to room temperature, continues reaction 12 hours; Question response adds the saturated NaCl aqueous solution, chloroform extraction after finishing, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and evaporate solvent and obtain crude product, at last with the crude product sherwood oil: ethyl acetate (v/v=15: 1) separate for leacheate carries out silica gel column chromatography, obtain pulverulent solids 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the 9-dioctyl fluorene, productive rate 65%, the GC-MS of this product (EI-m/z): 642 (M
+);
2) contain fluorenes, anthracene and diazosulfide unit multipolymer I
1Preparation, its reaction is shown below:
The preparation detailed process is: add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-dibromoanthracene 0.1mmol, 4,7-two bromo-2,1, the Na of 3-diazosulfide 0.9mmol, tetra-triphenylphosphine palladium 0.025mmol, 2mol/L
2CO
3Aqueous solution 5ml and toluene solvant 30ml are by repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, behind reaction 72h under 95 ℃ of conditions, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is concentrated into polymkeric substance/toluene solution about about 5ml, concentrated solution is splashed into constantly stirring in the 300ml anhydrous methanol, and there is solid precipitation to separate out, solid is through suction filtration, obtain pressed powder after the oven dry, again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to the surplus 5ml, splash into it in methanol solvate and stirred 6 hours, at last with polymkeric substance I
1Collect oven dry, with Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight, with the polymkeric substance I after purifying
1Carry out the GPC test, the number-average molecular weight Mn ≈ 69300 of this polymkeric substance, the polymkeric substance monodispersity is 1.86.
Embodiment 2
Contain fluorenes, anthracene and diazosulfide unit multipolymer I
2Preparation, its structural formula is as follows:
In the formula, x=0.8; Y=0.2.
Its preparation comprises the steps:
1) 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its concrete preparation process sees the step (1) among the embodiment 1 for details;
2) polymkeric substance I
2Preparation, its reaction is shown below:
The preparation detailed process is: add 2,7-two (4,4 in reactor, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 0.8mmol, 4,7-two bromo-2,1,3-diazosulfide 0.2mmol, Pd (PPh
3)
2Cl
20.02mmol, the NaHCO of 2mol/L
3Aqueous solution 10ml and ether solvent 40ml are by repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, behind reaction 48h under 80 ℃ of conditions, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is concentrated with polymkeric substance/toluene solution, concentrated solution is splashed in the 300ml anhydrous methanol, and uninterrupted the stirring, there is solid precipitation to separate out, obtain pressed powder after solid process suction filtration, the oven dry, again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyst P d (PPh
3)
2Cl
2, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred 4 hours, at last with polymkeric substance I
2Collect oven dry, with Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight, with the polymkeric substance I after purifying
2Carry out the GPC test, the number-average molecular weight Mn ≈ 42100 of this polymkeric substance, the polymkeric substance monodispersity is 1.76.
Embodiment 3
Contain fluorenes, anthracene and diazosulfide unit multipolymer I
3Preparation, its structural formula is as follows:
In the formula, x=0.5; Y=0.5.
Its preparation comprises the steps:
1) 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its preparation process sees the step (1) among the embodiment 1 for details.
2) polymkeric substance I
3Preparation, its reaction is shown below:
The preparation detailed process is: add 2,7-two (4,4,5,5-tetramethyl--1 in reactor, 3,2-, two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-dibromoanthracene 0.5mmol, 4,7-two bromo-5, the two tetradecyloxyanilines-2,1 of 6-, 3-diazosulfide 0.5mmol, Pd
2(dba)
3/ P (o-Tol)
30.022mmol, the NaOH aqueous solution 10ml of 2mol/L and 1: 1 by volume methylene dichloride and ethyl acetate mixed solvent 40ml, make reaction system be in anaerobic state by repeatedly leading to argon gas and vacuumizing, behind reaction 12h under 90 ℃ of conditions, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is concentrated into polymkeric substance/toluene solution about about 5ml, concentrated solution is splashed into constantly stirring in the 400ml dehydrated alcohol, and there is solid precipitation to separate out, solid is through suction filtration, obtain pressed powder after the oven dry, again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, polymkeric substance/chloroformic solution is revolved steam to remaining about 5ml at last, splash into it in alcohol solvent and stirred 5 hours, at last with polymkeric substance I
3Collect oven dry, with Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight, with the polymkeric substance I after purifying
3Carry out the GPC test, the number-average molecular weight Mn ≈ 69600 of this polymkeric substance, the polymkeric substance monodispersity is 1.53.
Embodiment 4
Contain fluorenes, anthracene and diazosulfide unit multipolymer I
4Preparation, its structural formula is as follows:
In the formula, x=0.5; Y=0.5.
Its preparation comprises the steps:
1) 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes, its reaction is shown below:
The preparation detailed process is: put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Protection under, add 2 of white, 7-two bromo-9 in the there-necked flask; 9-didecyl fluorenes 9.0mmol injects 1: 2 by volume refining ether of 200ml and the mixed solvent of trichloromethane with syringe again, slowly injects the phenyl lithium of 25.0mmol under-85 ℃ of conditions with syringe again; behind the stirring reaction 2 hours, under-85 ℃ of conditions, inject the 2-isopropoxy-4 of 28.0mmol with syringe; 4; 5,5-tetramethyl--1,3; 2-two assorted oxygen pentaboranes; be warmed up to room temperature reaction 15 hours, question response adds the saturated NaCl aqueous solution after finishing; adopt chloroform extraction; anhydrous sodium sulfate drying with filtrate collection and revolve and evaporate solvent, is that leacheate carries out silica gel column chromatography and separates with crude product with the mixed solvent of sherwood oil and ethyl acetate at last after filtering; obtain pulverulent solids 2; 7-two (4,4,5; 5-tetramethyl--1; 3,2-, two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes; productive rate 71%, the GC-MS of this product (EI-m/z): 699 (M
+);
2) polymkeric substance I
4Preparation, its reaction is shown below:
The preparation detailed process is: add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 0.5mmol, 4,7-two bromo-5, the two tetradecyloxyanilines-2,1 of 6-, 3-diazosulfide 0.5mmol, tetra-triphenylphosphine palladium 0.025mmol, the tetraethyl ammonium hydroxide aqueous solution 10ml of 2mol/L and toluene solvant 40ml, make reaction system be in anaerobic state by repeatedly leading to argon gas and vacuumizing, behind reaction 60h under 60 ℃ of conditions, in the reaction flask of product, add deionized water, and adopt toluene to extract, get organic phase, method with underpressure distillation is concentrated with polymkeric substance/toluene solution, concentrated solution is splashed in the 400ml dehydrated alcohol, and constantly stir, in whipping process, there is solid precipitation to separate out, solid is through suction filtration, obtain pressed powder after the oven dry, again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to the surplus 5ml, splash into it in alcohol solvent and stirred 8 hours, at last with polymkeric substance I
4Collect oven dry, with Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.With the polymkeric substance I after purifying
4Carry out the GPC test, the number-average molecular weight Mn ≈ 34100 of this product, the polymkeric substance monodispersity is 2.17.
Application Example 5
Contain fluorenes, anthracene and diazosulfide unit multipolymer I with embodiment 1 preparation
1Preparation as the solar cell device of active coating:
See also Fig. 2, this solar cell device comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14, the negative electrode 15 that stacks gradually, middle supplementary layer 13 adopts polyethylene dioxy base thiophene: polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS), active coating 14 comprises electron donor material and electron acceptor material, and electron donor material adopts and contains fluorenes, anthracene and diazosulfide unit multipolymer I
1, electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (referred to as PCBM).Transparent anode 12 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc.Wherein, glass-base 11 can be used as bottom, during making, chooses ito glass, and after ultrasonic cleaning, processes with oxygen-Plasma, and supplementary layer 13 in the middle of ito glass applies will contain fluorenes, anthracene and diazosulfide unit multipolymer I again
1On the supplementary layer 13, form active coating 14, and then by vacuum evaporation technology deposition cathode 15 on active coating 14, obtain above-mentioned solar cell device in the middle of being coated on after by blend with electron acceptor material.In a preferred embodiment, the thickness of transparent anode 12, middle supplementary layer 13, active coating 14, double-metal layer Ca and Al layer be respectively 180,30,200,80nm.
As shown in Figure 2, under illumination, light transmission glass-base 11 and ITO electrode 12 contain fluorenes, anthracene and diazosulfide unit multipolymer I in the active coating 14
1Absorbing light energy, and produce exciton, these excitons are moved to electron donor(ED)/acceptor material at the interface again, and with transfer transport to electron acceptor material, such as PCBM, realize the separation of electric charge, thereby form freely current carrier, be i.e. freely electronics and hole.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode, the hole is along electron donor material to ito anode transmission and collected by anode freely, thereby forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load 16, can power to it.In this process, contain fluorenes, anthracene and diazosulfide unit multipolymer I
1Because it has very wide spectral response range, can utilize more fully luminous energy, to obtain higher photoelectric transformation efficiency, increase the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, is convenient to large batch of preparation.With this device with epoxy encapsulation after, place under 110 ℃ of air tight conditions annealing 4 hours, drop to again room temperature.Because after device was annealed, the chemical structure of material was more regular in order, has improved transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Application Example 6
Contain fluorenes, anthracene and diazosulfide unit multipolymer I with embodiment 1 preparation
1The preparation of organic electroluminescence device:
See also Fig. 3, show to adopt to contain fluorenes, anthracene and diazosulfide unit multipolymer I
1Organic electroluminescence device, it comprises glass-base 21, transparent anode 22, luminescent layer 23, buffer layer 24, the negative electrode 25 that is cascading.Transparent anode 22 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Luminescent layer 23 comprises and contains fluorenes, anthracene and diazosulfide unit multipolymer I
1Buffer layer 24 can adopt LiF etc., but is not limited to this.Negative electrode 25 can be but be not limited to metal A l etc.Thereby in a specific embodiment, the organic electroluminescence device representation is: ITO/ contains fluorenes, anthracene and diazosulfide unit multipolymer I
1/ LiF/Al.Each layer can adopt existing method to form, and contains fluorenes, anthracene and diazosulfide unit multipolymer I
1Can be formed on the ITO by spin coating technique.On this luminescent layer, can adopt vacuum evaporation LiF buffer layer, on buffer layer, can adopt evaporation metal Al, as the negative electrode of device.
Application Example 7
See also Fig. 4, this organic field effect tube comprises substrate 31, insulation layer 32, decorative layer 33, the organic semiconductor layer 34 that is cascading and is located at source electrode 35 and drain electrode 36 on the organic semiconductor layer 34.Wherein, substrate 31 can be but be not limited to highly doped silicon chip (Si) that insulation layer 32 can be but be not limited to micro-nano (such as 500nm) thick SiO
2 Organic semiconductor layer 34 adopts and contains fluorenes, anthracene and diazosulfide unit multipolymer I
1Source electrode 35 and drain electrode 36 all can adopt but be not limited to gold.Decorative layer 33 can be but be not limited to octadecyl trichlorosilane alkane (OTS).Substrate 31, insulation layer 32, decorative layer 33 and source electrode 35 and drain electrode 36 all can adopt existing method to form.Organic semiconductor layer 34 can be to contain fluorenes, anthracene and diazosulfide unit multipolymer I
1Be spun on the insulation layer 32 of being modified by decorative layer 33.
The above only is preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind contains fluorenes, anthracene and diazosulfide unit multipolymer, and its general formula of molecular structure is following (I):
In the formula, n is the polymerization degree, and is 1～500 natural number; M is natural number, and 1≤m≤20; X, y are real positive value, and x+y=1; R
1, R
2Be selected from hydrogen atom, halogen, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted aryl, perhaps optional the replacement or unsubstituted heteroaryl; R
3Be selected from hydrogen atom, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted C
1～C
40Alkoxyl group, the optional replacement or unsubstituted C
6～C
40Aryl, the optional replacement or unsubstituted C
6～C
40Aralkyl, perhaps optional the replacement or unsubstituted C
6～C
40Alkoxy aryl.
2. fluorenes, anthracene and the diazosulfide unit multipolymer of containing according to claim 1 is characterized in that: described R
1, R
2Be selected from optional the replacement or unsubstituted C
1～C
40Alkyl; R
3Be selected from optional the replacement or unsubstituted C
1～C
40Alkoxyl group.
3. one kind contains fluorenes, anthracene and diazosulfide unit multipolymer preparation method, comprises the steps:
The compd A, B, the C that provide respectively following structural formula to represent,
Wherein, m is natural number, and 1≤m≤20; R
1, R
2Be selected from hydrogen atom, halogen, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted aryl or optional the replacement or unsubstituted heteroaryl; R
3Be selected from hydrogen atom, cyano group, the optional replacement or unsubstituted C
1～C
40Alkyl, the optional replacement or unsubstituted C
1～C
40Alkoxyl group, the optional replacement or unsubstituted C
6～C
40Aryl, the optional replacement or unsubstituted C
6～C
40Aralkyl, the optional replacement or unsubstituted C
6～C4
0Alkoxy aryl;
In the system of anhydrous, oxygen-free environment and organic solvent, with alkyl derivative and the 2-isopropoxy-4,4 of compd A, lithium, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes react, and generate compound 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes;
In anaerobic and alkaline environment and under the condition of catalyzer and organic solvent existence, with compound 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes, compd B and Compound C are carried out the Suzuki reaction, obtain following general structure and be that I represents contains fluorenes, anthracene and diazosulfide unit multipolymer
In the formula, x, y are real positive value, and x+y=1; N is the polymerization degree, and value is 1～500 natural number.
4. the fluorenes that contains according to claim 3, anthracene and diazosulfide unit multipolymer preparation method is characterized in that: described compound 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes preparation method is: anhydrous, in the system of oxygen-free environment and organic solvent, alkyl derivative with compd A and lithium reacts first, then add 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaboranes react and obtain described compound 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes product.
5. according to claim 3 or 4 described fluorenes, anthracene and the diazosulfide unit multipolymer preparation methods of containing, it is characterized in that: described compound 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9, in the 9-dialkyl group fluorenes preparation process, the alkyl derivative of compd A, lithium and 2-isopropoxy-4,4,5,5-tetramethyl--1, the mol ratio of 3,2-, two assorted oxygen pentaborane three reactants is 1.0: 2.0～4.0: 2.0～4.0; Described organic solvent is at least a in tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate; The temperature of reaction of this step is-70 ℃～-85 ℃, and the time is 12～48 hours.
6. according to claim 3 or 4 described fluorenes, anthracene and the diazosulfide unit multipolymer preparation methods of containing, it is characterized in that: described compound 2,7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane bases of 2-two)-9, in the 9-dialkyl group fluorenes preparation process, the alkyl derivative of lithium is at least a in n-Butyl Lithium, tert-butyl lithium, lithium methide, the phenyl lithium.
7. fluorenes, anthracene and the diazosulfide unit multipolymer preparation method of containing according to claim 3, it is characterized in that: in the described Suzuki reactions steps, catalyst loading is described compound 2,7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9,0.5%～15% of 9-dialkyl group fluorenes mole dosage;
Described catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand.
8. fluorenes, anthracene and the diazosulfide unit multipolymer preparation method of containing according to claim 3, it is characterized in that: in the described Suzuki reactions steps, the addition of alkali and described compound 2 in the alkaline environment, 7-two (4,4,5,5-tetramethyl--1,3,2-, two assorted oxygen pentaborane bases)-9, the mol ratio of 9-dialkyl group fluorenes is 5～10: 1;
Described alkali is at least a in alkali metal hydroxide, alkaline carbonate, the tetraethyl ammonium hydroxide.
9. fluorenes, anthracene and the diazosulfide unit multipolymer preparation method of containing according to claim 3 is characterized in that: in the described Suzuki reactions steps, and compound 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9, the mol ratio of 9-dialkyl group fluorenes, compd B and Compound C three reactants is m: p: q, wherein m=p+q, and m＞p＞0, m＞q＞0;
Described organic solvent is one or more in toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or the ethyl acetate;
The temperature of described Suzuki reaction is 60～95 ℃, and the reaction times is 12～72 hours.
According to claim 1 to 2 each described contain fluorenes, anthracene and diazosulfide unit multipolymer at polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties or/and the application in the organic laser apparatus.
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