CN102260371B - Organic copolymer, its preparation method and its application - Google Patents
Organic copolymer, its preparation method and its application Download PDFInfo
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- CN102260371B CN102260371B CN 201010190118 CN201010190118A CN102260371B CN 102260371 B CN102260371 B CN 102260371B CN 201010190118 CN201010190118 CN 201010190118 CN 201010190118 A CN201010190118 A CN 201010190118A CN 102260371 B CN102260371 B CN 102260371B
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- BRUOAURMAFDGLP-UHFFFAOYSA-N Brc(c1c2cccc1)c(cccc1)c1c2Br Chemical compound Brc(c1c2cccc1)c(cccc1)c1c2Br BRUOAURMAFDGLP-UHFFFAOYSA-N 0.000 description 2
- IPWKHHSGDUIRAH-UHFFFAOYSA-N CC1(C)OB(B2OC(C)(C)C(C)(C)O2)OC1(C)C Chemical compound CC1(C)OB(B2OC(C)(C)C(C)(C)O2)OC1(C)C IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 2
- CUPOOAWTRIURFT-UHFFFAOYSA-N N#Cc1ccc[s]1 Chemical compound N#Cc1ccc[s]1 CUPOOAWTRIURFT-UHFFFAOYSA-N 0.000 description 2
- 0 C*1OB(c2c(cccc3)c3c(B3OC(C)(C)C(C)(C)O3)c3ccccc23)OC1(C)C Chemical compound C*1OB(c2c(cccc3)c3c(B3OC(C)(C)C(C)(C)O3)c3ccccc23)OC1(C)C 0.000 description 1
- WZQOVZJEWJVWIZ-UHFFFAOYSA-N CC(C)(C(C)(C)O1)OB1S1OC(C)(C)C(C)(C)O1 Chemical compound CC(C)(C(C)(C)O1)OB1S1OC(C)(C)C(C)(C)O1 WZQOVZJEWJVWIZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention is applied to the technical field of the organic photoelectricity, and provides an organic copolymer, a preparation method and an application. The organic copolymer has a structural formula expressed as (I). The organic copolymer of the present invention is polymerized by anthracene or derivative group thereof and pyrrolo-pyrrole diketo or a derivative thereof, and is melted and polymerized the performances of anthracene or the derivative thereof and pyrrolo-pyrrole diketo or the derivative thereof. The organic copolymer has high stability to light, heat and different climates, and is capable of dissolving in a plurality of organic solvents, and has the advantages of excellent film forming ability, excellent current carrier transport performance and wide sunshine absorbing scope.
Description
Technical field
The invention belongs to the organic photoelectric technical field, relate in particular to a kind of organic copolymer, its preparation method and application.
Background technology
The pyrrolo-pyrrole-dione or derivatives thereof has high stability to light, heat and different weathers, but in the prior art, organic semiconductor material by the preparation of pyrrolo-pyrrole-dione or derivatives thereof, its film-forming properties, sunlight absorption region, carrier transport and in organic solvent solvability all undesirable, this has limited greatly by the application of pyrrolo-pyrrole-dione or derivatives thereof in the organic photoelectric technical field, becomes to hinder the huge obstacle that the pyrrolo-pyrrole-dione or derivatives thereof is used in the organic photoelectric technical field.
Summary of the invention
The purpose of the embodiment of the invention is to provide a kind of organic copolymer, and it is poor by organic semiconductor material film-forming properties, the carrier transport of the preparation of pyrrolo-pyrrole-dione or derivatives thereof to be intended to solve in the prior art, the technical problem that the sunlight absorption region is narrow.
Embodiments of the invention are achieved in that
A kind of organic copolymer, this organic copolymer have following structural formula (I):
Wherein, n is the natural number of 1-200,
R
1, R
2For identical or different, be selected from hydrogen, halogen, cyano group, C
1-C
40Alkyl, aryl or heteroaryl;
R
3, R
4For identical or different, be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl;
R
5, R
6For identical or different, be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl.
Another object of the present invention is to provide a kind of organic copolymer preparation method, this preparation method comprises the steps:
The anthracene derivant of following structural formula (II) expression and the pyrrolo-pyrrole-dione derivative of structural formula (III) expression are provided respectively;
Under the oxygen free condition, with the pyrrolo-pyrrole-dione derivative of the anthracene derivant of following structural formula (II) expression and structural formula (III) expression under 60-100 ℃ of temperature, under catalyzer, alkaline agent and organic solvent condition, carry out the Suzuki reaction, reacted 12-72 hour, obtain the organic copolymer of structural formula (I) expression, the Suzuki reaction formula is as follows:
(II) (III) (I)
Wherein, n is the natural number of 1-200,
R
1, R
2For identical or different, be selected from hydrogen, halogen, cyano group, C
1-C
40Alkyl, aryl or heteroaryl;
R
3, R
4For identical or different, be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl;
R
5, R
6For identical or different, be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl.
Further aim of the present invention is to provide the application of a kind of organic copolymer in preparation organic photoelectrical material, organic solar batteries device, organic field effect tube device, organic electroluminescence device, organic light storage device and organic laser apparatus, and the structural formula of this organic copolymer is:
Wherein, n is the natural number of 1-200,
R
1, R
2For identical or different, be selected from hydrogen, halogen, cyano group, C
1-C
40Alkyl, aryl or heteroaryl;
R
3, R
4For identical or different, be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl;
R
5, R
6For identical or different, be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl.
The organic copolymer of the embodiment of the invention is polymerized by the group of anthracene or derivatives thereof group, pyrrolo-pyrrole-dione or derivatives thereof, the anthracene or derivatives thereof has good stability and film-forming properties, absorption region to sunlight is very wide, possess simultaneously good carrier transport, the pyrrolo-pyrrole-dione or derivatives thereof has excellent stability to light, heat and different weathers.The organic copolymer of the embodiment of the invention melts the performance of having gathered anthracene or derivatives thereof, pyrrolo-pyrrole-dione or derivatives thereof, light, heat and different weathers had high stability, can be dissolved in multiple organic solvent, have excellent film-forming properties, carrier transport, and have wider sunlight absorption region.
Description of drawings
Fig. 1 be the embodiment of the invention provide the organic copolymer structural formula;
Fig. 2 be the embodiment of the invention provide with the structure iron of organic copolymer P1 as the organic solar batteries device of active layer material;
Fig. 3 show that the embodiment of the invention provides with the structure iron of organic copolymer P1 as the organic electroluminescence device of luminescent layer;
Fig. 4 show that the embodiment of the invention provides with the structure iron of organic copolymer P1 as the organic field effect tube of organic semiconductor layer.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, 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.
The organic copolymer of the embodiment of the invention uses anthracene or derivatives thereof, pyrrolo-pyrrole-dione or derivatives thereof as the structural unit of multipolymer, so that this organic copolymer possesses high stability to light, heat and different weathers, can be dissolved in multiple organic solvent, have excellent film-forming properties, carrier transport, and have wider sunlight absorption region.
The organic copolymer of the embodiment of the invention
Fig. 1 shows the structural formula (I) of the organic copolymer that the embodiment of the invention provides:
Wherein, n is the natural number of 1-200, is preferably the natural number of 10-100;
R
1, R
2For improving the group of solubility property in organic solvent, also be R
1, R
2Can improve and have R
1, R
2The solvability of the compound of group in organic solvent for example can be selected from hydrogen, halogen, cyano group, have C
1-C
40The alkyl of atom, aryl, heteroaryl, the various groups of selecting can be optional replace or unsubstituted, and alkyl comprises straight chain, with the alkyl of side chain or ring-type, the replacement that this place is said or replace and refer to that the hydrogen atom of this group itself is substituted or is not substituted.R
1, R
2Be preferably hydrogen or C
18-C
40Alkyl.R
1, R
2Can be identical or different.
R
3, R
4For improving the group of solubility property in organic solvent, also be R
3, R
4Can improve and have R
3, R
4The solvability of the compound of group in organic solvent for example can be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl, the various groups of selecting can be optional replace or unsubstituted, alkyl comprises straight chain, with the alkyl of side chain or ring-type, the replacement that this place is said or replace and refer to that the hydrogen atom of this group itself is substituted or is not substituted, R
3, R
4Be preferably C
8-C
20Alkyl.R
3, R
4Can be identical or different
R
5, R
6For improving the group of solubility property in organic solvent, also be R
5, R
6Can improve and have R
5, R
6The solvability of the compound of group in organic solvent for example can be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl, the various groups of selecting can be optional replace or unsubstituted, alkyl comprises straight chain, with the alkyl of side chain or ring-type.The replacement that this place is said or replace and refer to that the hydrogen atom of this group itself is substituted or is not substituted, R
5, R
6Be preferably hydrogen, C
6-C
20Alkoxyl group.R
5, R
6Can be identical also can be different.
The preparation method of the organic copolymer of the embodiment of the invention
The organic copolymer preparation method that the embodiment of the invention provides, this preparation method comprises the steps:
The anthracene derivant of following structural formula (II) expression and the pyrrolo-pyrrole-dione derivative of structural formula (III) expression are provided respectively;
Under the oxygen free condition, with the pyrrolo-pyrrole-dione derivative of the anthracene derivant of structural formula (II) expression and structural formula (III) expression under 60-100 ℃ of temperature, under catalyzer, alkaline agent and organic solvent condition, carry out the Suzuki reaction, reacted 12-72 hour, obtain the organic copolymer of structural formula (I) expression, this reaction formula is as follows:
Wherein, n is the natural number of 1-200,
R
1, R
2For identical or different, be selected from hydrogen, halogen, cyano group, C
1-C
40Alkyl, aryl or heteroaryl;
R
3, R
4For identical or different, be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl;
R
5, R
6For identical or different, be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl.
Wherein, n is the natural number of 1-200, is preferably the natural number of 10-100;
The employed catalyzer of this preparation method comprises Pd (PPh
3)
4, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (PPh
3)
2Cl
2Be the 0.5%-10% of molar weight of the anthracene derivant of structural formula (II) expression Deng, the usage quantity of catalyzer.
Employed alkaline agent comprises aqueous sodium hydroxide solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution or the tetraethyl ammonium hydroxide aqueous solution among this preparation method, in the alkaline agent, the usage quantity of alkaline substance such as sodium hydroxide, yellow soda ash, sodium bicarbonate or tetraethyl ammonium hydroxide be structural formula (II) expression anthracene derivant molar weight 5-10 doubly.
Oxygen free condition among this preparation method comprises various oxygen free conditions; such as thinking the environment such as 100% nitrogen, argon gas, carbonic acid gas; the preparation method of oxygen free condition also can comprise the whole bag of tricks; but preferably vacuumize by oil pump; pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of nitrogen; simultaneously when adding reactant to reaction system, the protection that keeps this nitrogen.
Employed organic solvent comprises various organic solvents among this preparation method, be preferably the organic solvent of the organic copolymer output that can improve structural formula (I) expression, such as thinking tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc.
The mol ratio of the pyrrolo-pyrrole-dione derivative of the anthracene derivant of employed structural formula (II) expression and structural formula (III) expression is 1 among this preparation method: 1-1: 4, be preferably 1: 1.
The preparation method of the anthracene derivant of the structural formula of the embodiment of the invention (II) expression
Among the organic copolymer preparation method of the embodiment of the invention, also comprise the preparation method of the anthracene derivant of structural formula (II) expression, comprise the steps:
Under the anhydrous and oxygen-free condition, anthracene derivant and the lithium alkylide of following structural formula (IV) expression are added in the organic solvent under-70 ℃ to-85 ℃ temperature, add two tetramethyl ethylene ketones and close two boron, temperature of reaction system is adjusted to 10-40 ℃ and keep this temperature, reacted 12-48 hour, obtain the anthracene derivant of structural formula (II) expression, the reaction formula of this step is expressed as:
The R of the embodiment of the invention
1, R
2Implication and the elaboration of front identical, no longer explain at this.
The acquisition of the oxygen free condition of the embodiment of the invention is identical with the elaboration of front, no longer explains at this.Anhydrous condition refers to that employed organic solvent, reactant and catalyzer etc. do not contain moisture among the anthracene derivant preparation method of structural formula (II) of the embodiment of the invention.
Can use various lithium alkylides among the anthracene derivant preparation method of this structural formula (II) expression, preferably n-Butyl Lithium.
The structural formula that the two tetramethyl ethylene ketones that use among the anthracene derivant preparation method of this structural formula (II) expression close two boron is:
The anthracene derivant of employed structural formula (IV) expression and the mol ratio of lithium alkylide are 1.0: 2.0 to 1.0: 4.0 among the anthracene derivant preparation method of this structural formula (II) expression, be preferably 1.0: 3.0, the molar weight that the employed pair of tetramethyl ethylene ketone closes two boron be structural formula (IV) expression the anthracene derivant molar weight 2.0-4.0 doubly.
Employed organic solvent comprises various organic solvents among the anthracene derivant preparation method of this structural formula (II) expression, preferably can improve the organic solvent of the anthracene derivant output of structural formula (II), such as thinking tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc., before the anthracene derivant preparation method of simultaneously this structural formula (II) expression begins, remove water treatment to organic solvent.By the water treatment that removes to organic solvent, the anthracene derivant output of structural formula (II) expression improves greatly.
Among the anthracene derivant preparation method of this structural formula (II) expression, the anthracene derivant of said structure formula (IV) expression and lithium alkylide reaction generate 9,10-, two lithium ion anthracenes, react after 1-8 hour, add two tetramethyl ethylene ketones again and close two boron.Add after two tetramethyl ethylene ketones close two boron, temperature of reaction system is adjusted to 10-40 ℃ and keep this temperature, continue again reaction 12-48 hour.
The pyrrolo-pyrrole-dione derivative preparation method of the structural formula of the embodiment of the invention (III) expression
Among the organic copolymer preparation method of the embodiment of the invention, also comprise the pyrrolo-pyrrole-dione derivative preparation method of structural formula (III) expression, comprise the steps:
S301: under the oxygen free condition, the 2-cyano thiophene derivative that will be represented by structure formula V and structural formula (VI) respectively is dissolved in the alcohol organic solvent, be under the 90-120 ℃ of condition in alkaline agent, temperature, add dimethyl succinate reaction 1-4 hour, obtain the derivative of the pyrrolo-pyrrole-dione of structural formula (VII) expression, the reaction formula of this step is expressed as:
S302: under the oxygen free condition, the pyrrolo-pyrrole-dione derivative of said structure formula (VII) expression is dissolved in the organic solvent, be under the 120-150 ℃ of condition in alkaline agent, temperature, the bromine substituent that adds the expression of following structural formula (VIII) and structural formula (IX), reacted 10-22 hour, obtain the pyrrolo-pyrrole-dione derivative of structural formula (X) expression, the reaction formula of this step is expressed as:
S303: under the condition of anaerobic, pyrrolo-pyrrole-dione derivative and the bromizating agent of said structure formula (X) expression are dissolved in the organic solvent, the lucifuge reaction is 20-60 hour under 10-40 ℃ of temperature, obtain the pyrrolo-pyrrole-dione derivative of said structure formula (III) expression, the reaction formula of this step is expressed as:
(X) (III)
The R of the embodiment of the invention
3, R
4, R
5, R
6Implication and the elaboration of front identical, no longer explain at this.The acquisition of the oxygen free condition of the embodiment of the invention is identical with the elaboration of front, no longer explains at this.
In the pyrrolo-pyrrole-dione derivative preparation method of this structural formula (III) expression, among the step S301, ratio by the molar weight of the integral molar quantity of the 2-cyano thiophene of structure formula V and structural formula (VI) expression and dimethyl succinate is 2-4 respectively: 1, the molar weight ratio of two kinds of cyano thiophenes is restriction not, and two kinds of 2-cyano thiophenes can be identical or different substituent cyano thiophenes.Alkaline agent can use various alkaline agents, is preferably potassium tert.-butoxide, and in the alkaline agent, the molar weight of alkaline substance is 1-2 times of above-mentioned 2-cyano thiophene integral molar quantity.Dimethyl succinate adopts the mode that dropwise adds to join in the reaction system, and the time of adding is 0.5-1 hour.
In the pyrrolo-pyrrole-dione derivative preparation method of this structural formula (III) expression, also comprise distilation steps among the step S301, be i.e. distill after step S301 reaction is finished, continue reaction 1-5 hour after the distillation.This distillation processing is to distill for the by-product carbinol with step 3 in the pyrrolo-pyrrole-dione derivative preparation method of this structural formula (III) expression.Process by distillation, the output of the derivative of the pyrrolo-pyrrole-dione of structural formula (VII) improves greatly.The organic solvent that uses in this step comprises various alcohol organic solvent, is preferably tertiary amyl alcohol.
In the pyrrolo-pyrrole-dione derivative preparation method of this structural formula (III) expression, among the step S302, the molar weight of the derivative of the pyrrolo-pyrrole-dione of structural formula (VIII) is 2-3 with the ratio of the mole total amount of the substituent of the bromine that is represented by structural formula (VIII) and structural formula (IX) respectively: 1, wherein, two kinds of bromine substituents can be identical or different substituent bromine substituents, alkaline agent can use various alkaline agents, Anhydrous potassium carbonate preferably, the consumption of alkaline agent does not have special requirement.The employed organic solvent of step S302 can be various organic solvents, is preferably DMF or tetrahydrofuran (THF).
If R
3And R
4When getting hydrogen simultaneously, the reaction of step S302 does not namely exist, and directly carries out step S303 behind step S301.
In the pyrrolo-pyrrole-dione derivative preparation method of this structural formula (III) expression, among the step S303, the derivative of the pyrrolo-pyrrole-dione of structural formula (X) expression and the molar ratio of bromizating agent are 1: 2-3.The reaction of step S303 is carried out 15-40 ℃ of lower lucifuge, and employed organic solvent comprises various organic solvents, preferably chloroform or methylene dichloride.
The application of the organic copolymer of the following structural formula (I) of the present embodiment
The application of a kind of organic copolymer in preparation organic photoelectrical material, organic solar batteries device, organic field effect tube device, organic electroluminescence device, organic light storage device and organic laser apparatus, the structural formula of this organic copolymer is:
Wherein, n is the natural number of 1-200, is preferably the natural number of 10-100;
R
1, R
2For improving the group of solubility property in organic solvent, also be R
1, R
2Can improve and have R
1, R
2The solvability of the compound of group in organic solvent for example can be selected from hydrogen, halogen, cyano group, have C
1-C
40The alkyl of atom, aryl, heteroaryl, the various groups of selecting can be optional replace or unsubstituted, and alkyl comprises straight chain, with the alkyl of side chain or ring-type, the replacement that this place is said or replace and refer to that the hydrogen atom of this group itself is substituted or is not substituted.R
1, R
2Be preferably hydrogen, C
18-C
40Alkyl.R
1, R
2Can be identical or different.
R
3, R
4For improving the group of solubility property in organic solvent, also be R
3, R
4Can improve and have R
3, R
4The solvability of the compound of group in organic solvent for example can be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl, the various groups of selecting can be optional replace or unsubstituted, alkyl comprises straight chain, with the alkyl of side chain or ring-type, the replacement that this place is said or replace and refer to that the hydrogen atom of this group itself is substituted or is not substituted, R
3, R
4Be preferably C
8-C
20Alkyl.R
3, R
4Can be identical or different.
R
5, R
6For improving the group of solubility property in organic solvent, also be R
5, R
6Can improve and have R
5, R
6The solvability of the compound of group in organic solvent for example can be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl, the various groups of selecting can be optional replace or unsubstituted, alkyl comprises straight chain, with the alkyl of side chain or ring-type.The replacement that this place is said or replace and refer to that the hydrogen atom of this group itself is substituted or is not substituted, R
5, R
6Be preferably hydrogen, C
6-C
20Alkoxyl group.R
5, R
6Can be identical also can be different.
The organic copolymer of the embodiment of the invention is polymerized by the group of anthracene or derivatives thereof group, pyrrolo-pyrrole-dione or derivatives thereof, the anthracene or derivatives thereof has good stability and film-forming properties, absorption region to sunlight is very wide, possess simultaneously good carrier transport, the pyrrolo-pyrrole-dione or derivatives thereof has excellent stability to light, heat and different weathers.The organic copolymer of the embodiment of the invention has stronger π-pi-conjugated and molecule hydrogen bond simultaneously.The organic copolymer of the embodiment of the invention melts the performance of having gathered anthracene or derivatives thereof, pyrrolo-pyrrole-dione or derivatives thereof, light, heat and different weathers had high stability, can be dissolved in multiple organic solvent, have excellent film-forming properties, carrier transport, and have wider sunlight absorption region.
Embodiment 1
The organic copolymer P1 of the present embodiment has following structural formula:
Wherein, n is the natural number of 1-200.
The preparation method of the organic copolymer P1 of the present embodiment comprises the steps:
Step 1, the basic anthracene of preparation 9,10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes)
Put up the tetrahydrofuran (THF) water distilling apparatus, vacuumize by oil pump, pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of nitrogen, simultaneously in reaction system adding reactant, the protection that also keeps this nitrogen.To join in the reactor of 1000mL through dry 5 days tetrahydrofuran (THF) of KOH, add sodium piece and benzophenone, and stir, when the system of being back to is intense violet color, collect tetrahydrofuran (THF).
Put up the anhydrous and oxygen-free reaction unit, vacuumize by oil pump, pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of nitrogen, simultaneously in reaction system adding reactant, the protection that also keeps this nitrogen.
With 9 of the light yellow crystal shape of 9.0mmol, the 10-dibromoanthracene joins in the reactor, add the tetrahydrofuran (THF) that obtains after the above-mentioned distillation of 150mL, the n-Butyl Lithium that under-75 ℃ of temperature, slowly adds 27.0mmol, temperature is remained on-75 ℃, stirring reaction 2 hours, system are gradually by the faint yellow orange that becomes.Add the two tetramethyl ethylene ketones of 30.6mmol again and close two boron, system is become faint yellow by orange, and temperature of reaction system is adjusted to 10-40 ℃ and keep this temperature, reacts 10-46 hour again.
Reaction adds saturated nacl aqueous solution after finishing in reacted liquid, add chloroform extraction, add anhydrous sodium sulfate drying, after carry out suction filtration, collect filtrate and revolve and evaporate solvent, obtain crude product, with the crude product sherwood oil: ethyl acetate (volume ratio is 15: 1) for leacheate carries out silica gel column chromatography, obtains 9,10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene, this step 9,10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes) productive rate of basic anthracene is 58%, and product is carried out gas phase/mass spectroscopy, obtains the result and is: GC-MS (EI-m/z): 430 (M
+),
The reaction formula of this step 1 is expressed as:
Step 2,3, the preparation of 6-dithienyl-pyrrolo-pyrrole-dione
Put up the anhydrous and oxygen-free reaction unit, vacuumize by oil pump, pass into again argon gas, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this argon gas.
In reactor, the potassium tert.-butoxide that adds 35.7mmol, the 2-cyano thiophene of 30.0mmol is dissolved in the tertiary amyl alcohol of 25.0mL and joins in this reactor, the temperature of reaction system is risen to 110 ℃ and keep this temperature to reaction to finish, slowly be added in the reactor after the dimethyl succinate of 10.0mmol being dissolved in the tertiary amyl alcohol of 8mL, joining day is 1 hour, reacts after the adding 1.5 hours again.And then the by-product carbinol in the reaction of this step 2 distilled out reactor, reacted again 2 hours.
Reaction system is cooled to 65 ℃, with the liquid behind the methyl alcohol diluting reaction of 50mL, add the acetic acid neutralization, refluxed 10 minutes, the reacted liquid of suction filtration again, obtain black solid, be that 30-70 ℃ methyl alcohol and deionized water washes respectively this black solid twice with temperature, in vacuum dry 10-30 minute, obtain above-mentioned 3,6-dithienyl-pyrrolo-pyrrole-dione, this step 3, the productive rate of 6-dithienyl-pyrrolo-pyrrole-dione is 78%, and product is carried out gas phase/mass spectroscopy, obtains the result to be: GC-MS (EI-m/z): 300 (M
+).
The reaction formula of this step 2 is expressed as:
Step 3,2,5-dioctyl-3, the preparation of 6-dithienyl-pyrrolo-pyrrole-dione
In reactor, vacuumize by oil pump, pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this nitrogen.
With 3 of 43.3mmol, 6-dithienyl-pyrrolo-pyrrole-dione and 24g Anhydrous potassium carbonate are dissolved in 250mLN, in the dinethylformamide solution, reaction system are warming up to 140 ℃ and keep this temperature to reaction to finish, add 200mmol 1-bromooctane, stirring reaction 16 hours.
Reaction system is cooled to 10-40 ℃, liquid after the reaction end is poured in the frozen water of 500mL, filter to collect and leach thing, to leach thing washes 3-10 time respectively with methyl alcohol and deionized water, in vacuum under 50-80 ℃ of temperature dry 1-3 hour, take methylene dichloride as leacheate dry thing is carried out silica gel column chromatography again, obtain above-mentioned 2,5-dioctyl-3,6-dithienyl-pyrrolo-pyrrole-dione, this step 2,5-dioctyl-3, the productive rate of 6-dithienyl-pyrrolo-pyrrole-dione is 71%, and product is carried out gas phase/mass spectroscopy, obtains the result to be: GC-MS (EI-m/z): 525 (M
+).
The reaction formula of this step 3 is expressed as:
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolo-pyrrole-dione
In reactor, vacuumize by oil pump, pass into again argon gas, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this argon gas.
With 2 of 8.6mmol, 5-dioctyl-3, the N-bromo-succinimide of 6-dithienyl-pyrrolo-pyrrole-dione and 17.6mmol is dissolved in the chloroform of 200mL, constantly stirs, and the lucifuge reaction is 50 hours under 10-40 ℃ of temperature.
Liquid after the reaction end is poured in the methanol solution of 200mL, filter after 30 minutes to collect and leach thing, with 50 ℃ washed with methanol 2 times, vacuum-drying 10-30 minute, take methylene dichloride as leacheate dried reactant being carried out silica gel column chromatography again separates, obtain above-mentioned 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolo-pyrrole-dione, this step 2,5-dioctyl-3, the productive rate of 6-two (5-bromothiophene) base-pyrrolo-pyrrole-dione is 75%, product is carried out gas phase/mass spectroscopy, obtain the result and be: GC-MS (EI-m/z): 682 (M
+).
The reaction formula of this step 4 is expressed as:
The preparation of step 5, organic copolymer P1
In reactor, vacuumize by oil pump, pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this nitrogen.
9-10-two (4,4,5 with 1mmol, 5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene, 2 of 1mmol, 5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolo-pyrrole-dione, 0.02mmol tetra-triphenylphosphine palladium, the sodium carbonate solution of the 2mol/L of 10mL, the 30mL methylbenzene was put in the reactor, 90 ℃ of lower reactions 72 hours.
After the reaction, in reactor, add deionized water and toluene extraction, get organic phase, with vacuum distillation method with this organic phase solution evaporate to dryness to 5mL, the organic phase solution after will distilling again joins in the 300mL methyl alcohol, has solid precipitation to separate out, precipitate one hour, get solid behind the suction filtration, and oven dry, pressed powder obtained.After again pressed powder being dissolved with chloroform, take methylene dichloride as leacheate, with solution neutral alumina chromatography column chromatographic separation, remove tetra-triphenylphosphine palladium, after polymkeric substance/chloroformic solution revolved steam to 5mL, add methyl alcohol and stirred 1-10 hour, at last polymer P 1 is collected, oven dry.With Soxhlet extractor with polymer P 1 extracting, to improve the monodispersity of polymer P 1.
Polymer P 1 after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 54100, the polymkeric substance monodispersity is 1.98.
The reaction formula of this step 5 is expressed as:
Embodiment 2
The organic copolymer P2 of the embodiment of the invention has following structural formula:
Wherein, n is the natural number of 1-200.
The preparation method of the organic copolymer P2 of the embodiment of the invention is as follows:
Step 1, the basic anthracene of preparation 9,10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes)
The preparation process of the basic anthracene of 9,10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes) is as described in embodiment 1 step 1.
Step 2,3, the preparation of 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione
Put up the anhydrous and oxygen-free reaction unit, vacuumize by oil pump, pass into again argon gas, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this argon gas.
In reactor, the potassium tert.-butoxide that adds 22mmol, the 4-hexyloxy of 20.0mmol-2-cyano thiophene is dissolved in the tertiary amyl alcohol of 20mL and joins in this reactor, the temperature of reaction system is risen to 110 ℃ and keep this temperature to reaction to finish, slowly be added in the reactor after the dimethyl succinate of 8.0mmol being dissolved in the tertiary amyl alcohol of 6mL, joining day is 1 hour, reacts after the adding 2 hours again.Again the by-product carbinol in this reaction is distilled out reaction system, continue reaction 2.5 hours.
Reaction system is cooled to 60 ℃, with the liquid after the methyl alcohol diluting reaction end of 50mL, add the acetic acid neutralization, refluxed 15 minutes, the reacted liquid of suction filtration again, obtain black solid, be that 30-70 ℃ methyl alcohol and deionized water washes respectively this black solid twice with temperature, in vacuum dry 10-30 minute, obtain above-mentioned 3,6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione, this step 3, the productive rate of 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione is 71%, and product is carried out gas phase/mass spectroscopy, obtains the result and is: GC-MS (EI-m/z): 501 (M
+).
The reaction formula of this step 2 is expressed as:
Step 3,2,5-dioctyl-3, the preparation of 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione
In reactor, vacuumize by oil pump, pass into again argon gas, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this argon gas.
With 3 of 43.3mmol, 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione and 24g Anhydrous potassium carbonate are dissolved in 250mLN, in the dinethylformamide solution, reaction system is warming up to 150 ℃ and keep this temperature to reaction to finish, added 1-bromooctane 200mmol stirring reaction 14 hours.
Reaction system is cooled to 10-40 ℃, liquid after the reaction end is poured in the frozen water of 500mL, filter to collect and leach thing, to leach thing usefulness methyl alcohol and deionized water rinsing 3-10 time, 50-80 ℃ was descended dry 1-3 hour in vacuum, take methylene dichloride as leacheate dry thing is carried out silica gel column chromatography again, obtain above-mentioned 2,5-dioctyl-3,6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione, this step 2,5-dioctyl-3, the productive rate of 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione is 69%, and product is carried out gas phase/mass spectroscopy, obtains the result and is: GC-MS (EI-m/z): 725 (M
+).
The reaction formula of this step 3 is expressed as:
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromo-4 hexyloxy thiophene) base-pyrrolo-pyrrole-dione
In reactor, vacuumize by oil pump, pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this nitrogen.
With 2 of 5mmol, 5-dioctyl-3, the N-bromo-succinimide of 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione and 14mmol is dissolved in the chloroform of 250mL, constantly stirs, in 10-40 ℃ of lower lucifuge reaction 30 hours.
Reaction liquid after the reaction end is poured in the methanol solution of 250mL, filter after 30 minutes to collect and leach thing, with 50 ℃ washed with methanol 2 times, vacuum-drying 10-30 minute, take methylene dichloride as leacheate dried reactant is carried out silica gel column chromatography again and separates, obtain above-mentioned 2,5-dioctyl-3,6-two (5-bromo-4 hexyloxy thiophene) base-pyrrolo-pyrrole-dione, the reaction formula of this step 4 is expressed as:
The preparation of step 5, organic copolymer P2
In reactor, vacuumize by oil pump, pass into again argon gas, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this argon gas.
With 9 of 1mmol, 10-two (4,4,5,5 ,-tetramethyl--1,3,2-, two assorted oxygen pentaboranes) basic anthracene, 2 of 1mmol, 5-dioctyl-3,6-two (5-bromo-4-hexyloxy thiophene) base-pyrrolo-pyrrole-dione, the tetra-triphenylphosphine palladium of 0.04mmol, the sodium carbonate solution of the 2mol/L of 10mL, the 30mL methylbenzene is put in the reactor, and reaction is 60 hours under 85 ℃ of temperature.
After the reaction, in reactor, add deionized water and toluene extraction, get organic phase, with vacuum distillation method with this organic phase solution evaporate to dryness to 5mL, the organic phase solution after will distilling again joins in the 300mL methyl alcohol, has solid precipitation to separate out, precipitate one hour, get solid behind the suction filtration, and oven dry, pressed powder obtained.After again pressed powder being dissolved with chloroform, take methylene dichloride as leacheate, with solution neutral alumina chromatography column chromatographic separation, remove tetra-triphenylphosphine palladium, after polymkeric substance/chloroformic solution revolved steam to 5mL, add methyl alcohol and stirred 1-10 hour, at last polymer P 2 is collected, oven dry.With Soxhlet extractor with polymer P 2 extractings, to improve the monodispersity of polymer P 2.
Polymer P 2 after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 45300, the polymkeric substance monodispersity is 2.08, the reaction formula of this step is expressed as:
Embodiment 3
The organic copolymer P3 of the embodiment of the invention has following structural formula:
Wherein, n is the natural number of 1-200.
The preparation method of the organic copolymer P3 of the embodiment of the invention is as follows:
Step 1, preparation 9,10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2,6-two (2-octyl-decyl) anthracene
Put up the tetrahydrofuran (THF) water distilling apparatus, vacuumize by oil pump, pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of nitrogen, simultaneously in reaction system adding reactant, the protection that also keeps this nitrogen.To join in the reactor of 1000mL through dry 6 days tetrahydrofuran (THF) of KOH, add sodium piece and benzophenone, and stir, when the system of being back to is intense violet color, collect tetrahydrofuran (THF).
Put up the anhydrous and oxygen-free reaction unit, vacuumize by oil pump, pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of nitrogen, simultaneously in reaction system adding reactant, the protection that also keeps this nitrogen.
With 9 of 5.0mmol, 10-two bromo-2, (this compou nd synthesis method is referring to the people's such as Klaus Mullen Macromol.Chem.Phys.2006 for 6-two (2-octyl-decyl) anthracene, 207,1107-1115) join in the reactor, add the tetrahydrofuran (THF) that obtains after the above-mentioned distillation of 150mL, the n-Butyl Lithium that under-80 ℃, slowly adds 15.0mmol, temperature is remained on-80 ℃, stirring reaction 2 hours adds the two tetramethyl ethylene ketones of 30.6mmol again and closes two boron.Temperature of reaction system is adjusted to 10-40 ℃ and keep this temperature, continues reaction 10-46 hour.
Reaction adds saturated nacl aqueous solution after finishing in reacted liquid, add chloroform extraction, add anhydrous sodium sulfate drying, after carry out suction filtration, collect filtrate and revolve and evaporate solvent, obtain crude product, with the crude product sherwood oil: ethyl acetate (volume ratio is 15: 1) for leacheate carries out silica gel column chromatography, obtains 9,10-two (4,4,5,5,-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2,6-two (2-octyl-decyl) anthracene, this step 9,10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2, the productive rate of 6-two (2-octyl-decyl) anthracene is 61%, and product is carried out gas phase/mass spectroscopy, obtains the result and is: GC-MS (EI-m/z): 935 (M
+).
The reaction formula of this step is expressed as:
Step 2,3, the preparation of 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione
The preparation process of 3,6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione is as described in embodiment 2 step 2.
Step 3,2,5-dioctyl-3, the preparation of 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione
2,5-dioctyl-3, the preparation process of 6-two (4-hexyloxy) thienyl-pyrrolo-pyrrole-dione is as described in embodiment 2 step 3.
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromo-4 hexyloxy thiophene) base-pyrrolo-pyrrole-dione
2,5-dioctyl-3, the preparation process of 6-two (5-bromo-4 hexyloxy thiophene) base-pyrrolo-pyrrole-dione is as described in embodiment 2 step 4.
The preparation of step 5, organic copolymer P1
In reactor, vacuumize by oil pump, pass into again nitrogen, 3-4 time so repeatedly, pass into again nitrogen always reaction system is under the protection of argon gas, simultaneously in reaction system adding reactant, the protection that also keeps this nitrogen.
9-10-two (4,4,5 with 1mmol, 5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2,6-two (2-octyl-decyl) anthracene, 2 of 1mmol, 5-dioctyl-3,6-two (5-bromo-4-hexyloxy thiophene) base-pyrrolo-pyrrole-dione, the tetra-triphenylphosphine palladium of 0.01mmol, the sodium carbonate solution of the 2mol/L of 8mL, the 40mL methylbenzene was put in the reactor, 85 ℃ of lower reactions 48 hours.
After the reaction, in reactor, add deionized water and toluene extraction, get organic phase, with vacuum distillation method with this organic phase solution evaporate to dryness to 5mL, the organic phase solution after will distilling again joins in the 300mL methyl alcohol, has solid precipitation to separate out, precipitate one hour, get solid behind the suction filtration, and oven dry, pressed powder obtained.After again pressed powder being dissolved with chloroform, take methylene dichloride as leacheate, with solution neutral alumina chromatography column chromatographic separation, remove tetra-triphenylphosphine palladium, after polymkeric substance/chloroformic solution revolved steam to 5mL, add methyl alcohol and stirred 1-10 hour, at last polymer P 3 is collected, oven dry.With Soxhlet extractor with polymer P 3 extractings, to improve the monodispersity of polymer P 3.
Polymer P 3 after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 75100, the polymkeric substance monodispersity is 1.78, the reaction formula of this step is expressed as:
Application Example 4
Fig. 2 shows the structure iron as the organic solar batteries device 40 of active layer material with the organic copolymer P1 of top embodiment 1, this organic solar batteries device architecture is: glass-base 41, transparent anode 42, middle supplementary layer 43, active coating 44, negative electrode 45, wherein, glass-base 41 can comprise various glass, to not restriction of material, but can not hinder sun optical transmission.Transparent anode 42 can for but be not limited to the tin indium oxide that square resistance is 10-20 Ω/mouth, i.e. ITO.Middle supplementary layer 43 can for but be not limited to PEDOT:PSS, PEDOT is poly-(3,4-Ethylenedioxy Thiophene), PSS is poly-(styrene sulfonic acid), comprises organic copolymer p 1 and (6,6) phenyl-C in the active coating 44
61-methyl-butyrate is PCBM, and wherein, organic copolymer P1 is the electron donor material of this organic solar batteries device 40, and PCBM is the electron acceptor material of this organic solar batteries device 40.In the organic solar batteries device 40 of the embodiment of the invention, glass-base 41/ transparent anode 42 is integral unit, is also referred to as ito glass, can buy from the market.
The preparation method of above-mentioned organic solar batteries device is as follows,
With organic copolymer P1 and PCBM take weight ratio as 1: 1-5: 1 is dissolved in the chloroform, stirs.With above-mentioned ito glass with ultrasonic cleaning after, middle supplementary layer 43 is applied on the transparent anode 42 by spin coating method.The mixing solutions of above-mentioned organic copolymer P1 and PCBM is passed through spin coating method, be applied to the upper surface of the middle supplementary layer 43 of above-mentioned ito glass, form active coating, pass through again vacuum deposition method, negative electrode 45 is plated on above-mentioned active coating 44, obtains the prefabrication of organic solar batteries device 40.With these organic solar batteries device 40 prefabrication epoxy encapsulation, under 110 ℃ of temperature, annealed 4 hours in the closed environment, be down to again room temperature, obtain the organic solar batteries device 40 of the embodiment of the invention.
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 5
Fig. 3 shows the organic electroluminescence device 50 as luminescent layer with the P1 of embodiment 1, this device 50 comprises glass 51 basic units, transparent anode 52, luminescent layer 53, buffer layer 54, negative electrode 55, wherein, glass 51 can be various glass, to not restriction of material, but can not hinder the transmission of light, transparent anode 52 can for but to be not limited to square resistance be that the tin indium oxide of 10-20 Ω/mouth is ITO, luminescent layer 53 with copolymer p 1 as luminescent material, adopt spin coating method to be applied on the transparent anode 52, the material of buffer layer 54 can for but be not limited to LiF, LiF adopts vacuum deposition method to be plated on the luminescent layer 53, negative electrode 55 can for but be not limited to the metallic aluminium material, be deposited on the buffer layer 54 by vacuum coating method.
In the embodiments of the invention, glass 51 and transparent anode 52 are structures of disjunctor, can buy in market.
Application Example 6
Fig. 4 shows the organic field effect tube that contains P1 60 with embodiment 1, and this transistor 60 comprises substrate 61, insulation layer 62, decorative layer 63, organic semiconductor layer 64, source electrode 65 and drain electrode 66.
The material that substrate 61 uses can for but be not limited to elementary silicon/silicon chip, the material of insulation layer 62 can for but be not limited to silicon-dioxide, thickness is 500mm, the material of decorative layer 63 can for but to be not limited to octadecyl trichlorosilane alkane be OTS, organic semiconductor layer 64 adopts spin coating methods to be applied on the decorative layer 63, the material of source electrode 65 and drain electrode 66 can for but be not limited to gold.
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. an organic copolymer is characterized in that, described organic copolymer has following structure formula I:
Wherein, n is the natural number of 1-200,
R
1, R
2For identical or different, be selected from hydrogen, halogen, cyano group, C
1-C
40Alkyl, aryl or heteroaryl;
R
3, R
4For identical or different, be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl;
R
5, R
6For identical or different, be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl.
2. organic copolymer as claimed in claim 1 is characterized in that, R
1, R
2Be hydrogen, C
18-C
40Alkyl, aryl or heteroaryl; R
3, R
4Be C
8-C
20Alkyl; R
5, R
6Be hydrogen or C
6-C
20Alkoxyl group.
3. organic copolymer preparation method, it comprises the steps:
The pyrrolo-pyrrole-dione derivative that provides respectively anthracene derivant that following structure formula II represents and structure formula III to represent;
Under the oxygen free condition, the pyrrolo-pyrrole-dione derivative that the anthracene derivant that following structure formula II is represented and structure formula III represent is under 60-100 ℃ of temperature, under catalyzer, alkaline agent and organic solvent condition, carry out the Suzuki reaction, reacted 12-72 hour, obtain the organic copolymer that the structure formula I represents, the Suzuki reaction formula is expressed as:
Wherein, n is the natural number of 1-200,
R
1, R
2For identical or different, be selected from hydrogen, halogen, cyano group, C
1-C
40Alkyl, aryl or heteroaryl;
R
3, R
4For identical or different, be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl;
R
5, R
6For identical or different, be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl.
4. organic copolymer preparation method as claimed in claim 3 is characterized in that, the mol ratio of described anthracene derivant and pyrrolo-pyrrole-dione derivative is 1: 1 to 1: 4; The molar weight of described catalyzer is the 0.5%-10% of the molar weight of the anthracene derivant that represents of structure formula II; The molar weight of described alkaline agent neutral and alkali thing be the structure formula II anthracene derivant molar weight 5-10 doubly.
5. the preparation method of organic copolymer as claimed in claim 3 is characterized in that, also comprises the preparation method of the anthracene derivant that the structure formula II represents:
Under the anhydrous and oxygen-free condition, anthracene derivant and lithium alkylide that following structure formula IV is represented are dissolved in organic solvent under-70 ℃ to-85 ℃ temperature, add two tetramethyl ethylene ketones and close two boron, temperature of reaction system is adjusted to 10-40 ℃ and keep this temperature, reacted 12-48 hour, obtain the anthracene derivant that the structure formula II represents, the reaction formula of this step is expressed as:
6. organic copolymer preparation method as claimed in claim 5 is characterized in that, the anthracene derivant that described structure formula IV represents and the mol ratio of lithium alkylide are 1.0: 2.0 to 1.0: 4.0; The anthracene derivant that described structure formula IV represents and lithium alkylide reaction added two tetramethyl ethylene ketones again and close two boron after 1-8 hour; The molar weight that the described pair of tetramethyl ethylene ketone closes two boron be the anthracene derivant molar weight that represents of structure formula IV 2.0-4.0 doubly.
7. organic copolymer preparation method as claimed in claim 3 is characterized in that, also comprises the preparation method of the pyrrolo-pyrrole-dione derivative that the structure formula III represents:
Under the oxygen free condition, the 2-cyano thiophene derivative that will be represented by structural formula (V) and structure formula VI respectively is dissolved in the organic solvent, be under the 90-120 ℃ of condition in alkaline agent, temperature, add dimethyl succinate reaction 1-4 hour, obtain the derivative of the pyrrolo-pyrrole-dione of structural formula (VII) expression, the reaction formula of this step is expressed as:
Under the oxygen free condition, the pyrrolo-pyrrole-dione derivative of said structure formula (VII) expression is dissolved in the organic solvent, be under the 120-150 ℃ of condition in alkaline agent, temperature, add the bromine substituent that is represented by following structural formula (VIII) and structural formula (IX) respectively, reacted 10-22 hour, obtain the pyrrolo-pyrrole-dione derivative of structural formula (X) expression, the reaction formula of this step is expressed as:
Under the condition of anaerobic, pyrrolo-pyrrole-dione derivative and the bromizating agent of said structure formula (X) expression are dissolved in the organic solvent, the lucifuge reaction is 20-60 hour under 10-40 ℃ of temperature, obtain the pyrrolo-pyrrole-dione derivative that the said structure formula III represents, the reaction formula of this step is expressed as:
8. organic copolymer preparation method as claimed in claim 7 is characterized in that, the ratio of the molar weight of the described 2-cyano thiophene integral molar quantity that is represented by structural formula (V) and structure formula VI respectively and dimethyl succinate is 2-4: 1; After the described 2-cyano thiophene that is represented by structural formula (V) and structure formula VI respectively and the dimethyl succinate reaction, with the reaction liquid distillation, continue reaction 1-5 hour; In the derivative preparation method of the pyrrolo-pyrrole-dione of described structural formula (VII) expression, the molar weight of alkaline agent neutral and alkali thing is 1-2 times of the 2-cyano thiophene integral molar quantity that represents of described structure formula (V) and structure formula VI; Described dimethyl succinate adopts the mode that dropwise adds to join in the reaction system, and the time of adding is 0.5-1 hour.
9. organic copolymer preparation method as claimed in claim 7, it is characterized in that, the molar weight of the derivative of the pyrrolo-pyrrole-dione of structural formula (VII) is 2-3 with the ratio of the mole total amount of the substituent of the bromine that is represented by structural formula (VIII) and structural formula (IX) respectively: 1; The pyrrolo-pyrrole-dione derivative of described structural formula (X) expression and the molar ratio of bromizating agent are 1: 2-3.
10. the application of organic copolymer in preparation organic photoelectrical material, organic solar batteries device, organic field effect tube device, organic electroluminescence device, organic light storage device and organic laser apparatus, the structural formula of this organic copolymer is:
Wherein, n is the natural number of 1-200,
R
1, R
2For identical or different, be selected from hydrogen, halogen, cyano group, C
1-C
40Alkyl, aryl or heteroaryl;
R
3, R
4For identical or different, be selected from hydrogen, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl;
R
5, R
6For identical or different, be selected from hydrogen, cyano group, C
1-C
20Alkyl, C
1-C
20Alkoxyl group, C
6-C
20Aryl, C
6-C
20Aralkyl, C
6-C
20Alkoxy aryl.
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| CN104211920A (en) * | 2013-05-29 | 2014-12-17 | 海洋王照明科技股份有限公司 | Conjugated polymer, preparation method and applications thereof |
| CN105742501B (en) * | 2016-05-03 | 2018-07-06 | 苏州大学 | Based on organic electrical storage device of ito glass substrate through phosphonic acids or trichlorosilane modification and preparation method thereof |
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| CN1977029A (en) * | 2004-06-29 | 2007-06-06 | 西巴特殊化学品控股有限公司 | Fluorescent quinacridones |
| CN101654517A (en) * | 2008-08-18 | 2010-02-24 | 施乐公司 | Semiconducting polymers |
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| CN1977029A (en) * | 2004-06-29 | 2007-06-06 | 西巴特殊化学品控股有限公司 | Fluorescent quinacridones |
| CN101654517A (en) * | 2008-08-18 | 2010-02-24 | 施乐公司 | Semiconducting polymers |
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