CN102260371A - Organic copolymer, its preparation method and its application - Google Patents
Organic copolymer, its preparation method and its application Download PDFInfo
- Publication number
- CN102260371A CN102260371A CN2010101901187A CN201010190118A CN102260371A CN 102260371 A CN102260371 A CN 102260371A CN 2010101901187 A CN2010101901187 A CN 2010101901187A CN 201010190118 A CN201010190118 A CN 201010190118A CN 102260371 A CN102260371 A CN 102260371A
- Authority
- CN
- China
- Prior art keywords
- organic
- reaction
- formula
- preparation
- structural formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 Cc1ccc(C(N(*)C(C2=C(c3ccc(*(*)*)[s]3)N3C)=O)=C2C3=O)[s]1 Chemical compound Cc1ccc(C(N(*)C(C2=C(c3ccc(*(*)*)[s]3)N3C)=O)=C2C3=O)[s]1 0.000 description 2
- 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
- ZLXSWNVYGSZXOP-UHFFFAOYSA-N CC1(C)OB(c2c(cccc3)c3c(B3OC(C)(C)C(C)(C)O3)c3c2cccc3)OC1(C)C Chemical compound CC1(C)OB(c2c(cccc3)c3c(B3OC(C)(C)C(C)(C)O3)c3c2cccc3)OC1(C)C ZLXSWNVYGSZXOP-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
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
Pyrrolopyrrole diketone or derivatives thereof has high stability to light, heat and different weathers, but in the prior art, organic semiconductor material by the preparation of pyrrolopyrrole diketone 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 pyrrolopyrrole diketone or derivatives thereof in the organic photoelectric technical field, becomes to hinder the huge obstacle that pyrrolopyrrole diketone 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 pyrrolopyrrole diketone 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 pyrrolopyrrole derovatives of structural formula (III) expression are provided respectively;
Under the oxygen free condition, with the pyrrolopyrrole derovatives 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, pyrrolopyrrole diketone or derivatives thereof, the anthracene or derivatives thereof has good stability and film-forming properties, absorption region to sunlight is very wide, possess good carrier transport simultaneously, pyrrolopyrrole diketone 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, pyrrolopyrrole diketone 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 the sunlight absorption region of broad.
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,, the present invention is further elaborated below in conjunction with drawings and Examples.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
The organic copolymer of the embodiment of the invention uses anthracene or derivatives thereof, the pyrrolopyrrole diketone or derivatives thereof structural unit as multipolymer, make this organic copolymer possess high stability to light, heat and different weathers, can be dissolved in multiple organic solvent, have excellent film-forming properties, carrier transport, and have the sunlight absorption region of broad.
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 for use can be optional replace or unsubstituted, and alkyl comprises straight chain, band side chain or cyclic alkyl, the replacement that this place is said or replace and be meant 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 for use can be optional replace or unsubstituted, alkyl comprises straight chain, band side chain or cyclic alkyl, the replacement that this place is said or replace and be meant 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 for use can be optional replace or unsubstituted, alkyl comprises straight chain, band side chain or cyclic alkyl.The replacement that this place is said or replace and be meant 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 pyrrolopyrrole derovatives of structural formula (III) expression are provided respectively;
Under the oxygen free condition, with the pyrrolopyrrole derovatives 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
2Deng, the usage quantity of catalyzer the 0.5%-10% of molar weight of the anthracene derivant of structural formula (II) expression.
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; for example can be 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; feed nitrogen again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of nitrogen gas; when reaction system adds reactant, keep this protection of nitrogen gas simultaneously.
Employed organic solvent comprises various organic solvents among this preparation method, is preferably the organic solvent of the organic copolymer output that can improve structural formula (I) expression, for example can be tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc.
The mol ratio of the pyrrolopyrrole derovatives 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, the 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
2The implication and the elaboration of front identical, no longer do explanation at this.
The acquisition of the oxygen free condition of the embodiment of the invention is identical with the elaboration of front, no longer does explanation at this.Anhydrous condition is meant 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), for example can be tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc., before the anthracene derivant preparation method of this structural formula (II) expression simultaneously 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, and 10-two lithium ion anthracenes reacted 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 reaction 12-48 hour again.
The pyrrolopyrrole derovatives 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 pyrrolopyrrole derovatives preparation method of structural formula (III) expression, comprise the steps:
S301: under the oxygen free condition, the 2-cyano thiophene derivative that to be represented by structure formula V and structural formula (VI) respectively is dissolved in the alcohol organic solvent, in alkaline agent, temperature is under the 90-120 ℃ of condition, add dimethyl succinate reaction 1-4 hour, obtain the derivative of the pyrrolopyrrole diketone of structural formula (VII) expression, the reaction formula of this step is expressed as:
S302: under the oxygen free condition, the pyrrolopyrrole derovatives of said structure formula (VII) expression is dissolved in the organic solvent, in alkaline agent, temperature is under the 120-150 ℃ of condition, the bromine substituent that adds the expression of following structural formula (VIII) and structural formula (IX), reacted 10-22 hour, obtain the pyrrolopyrrole derovatives of structural formula (X) expression, the reaction formula of this step is expressed as:
S303: under the condition of anaerobic, the pyrrolopyrrole derovatives 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 pyrrolopyrrole derovatives 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
6The implication and the elaboration of front identical, no longer do explanation at this.The acquisition of the oxygen free condition of the embodiment of the invention is identical with the elaboration of front, no longer does explanation at this.
Among the pyrrolopyrrole derovatives 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 without limits, 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 a 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.
Among the pyrrolopyrrole derovatives 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 that reaction 1-5 hour is continued in the distillation back.This distillation processing is to distill for the by-product carbinol with step 3 among the pyrrolopyrrole derovatives preparation method of this structural formula (III) expression.Handle by distillation, the output of the derivative of the pyrrolopyrrole diketone of structural formula (VII) improves greatly.The organic solvent that uses in this step comprises various alcohol organic solvent, is preferably tertiary amyl alcohol.
Among the pyrrolopyrrole derovatives preparation method of this structural formula (III) expression, among the step S302, the molar weight of the derivative of the pyrrolopyrrole diketone of structural formula (VIII) is 2-3 with the ratio of the mole total amount of the substituent of the bromine of being 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 preferably N for various organic solvents, dinethylformamide or tetrahydrofuran (THF).
If R
3And R
4When getting hydrogen simultaneously, the reaction of step S302 does not promptly exist, and directly carries out step S303 behind step S301.
Among the pyrrolopyrrole derovatives preparation method of this structural formula (III) expression, among the step S303, the derivative of the pyrrolopyrrole diketone of structural formula (X) expression and the molar ratio of bromizating agent are 1: 2-3.The 15-40 ℃ of following lucifuge that be reflected at of step S303 carried out, 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 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 for use can be optional replace or unsubstituted, and alkyl comprises straight chain, band side chain or cyclic alkyl, the replacement that this place is said or replace and be meant 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 for use can be optional replace or unsubstituted, alkyl comprises straight chain, band side chain or cyclic alkyl, the replacement that this place is said or replace and be meant 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 for use can be optional replace or unsubstituted, alkyl comprises straight chain, band side chain or cyclic alkyl.The replacement that this place is said or replace and be meant 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, pyrrolopyrrole diketone or derivatives thereof, the anthracene or derivatives thereof has good stability and film-forming properties, absorption region to sunlight is very wide, possess good carrier transport simultaneously, pyrrolopyrrole diketone 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, pyrrolopyrrole diketone 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 the sunlight absorption region of broad.
Embodiment 1
The organic copolymer P1 of present embodiment has following structural formula:
Wherein, n is the natural number of 1-200.
The preparation method of the organic copolymer P1 of present embodiment comprises the steps:
Step 1, preparation 9, the basic anthracene of 10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes)
Put up the tetrahydrofuran (THF) water distilling apparatus, vacuumize, feed nitrogen again by oil pump, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of nitrogen gas, when reaction system adds reactant, also keep this protection of nitrogen gas simultaneously.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, feed nitrogen again by oil pump, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of nitrogen gas, when reaction system adds reactant, also keep this protection of nitrogen gas simultaneously.
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 steam 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-pyrrolopyrrole diketone
Put up the anhydrous and oxygen-free reaction unit, vacuumize, feed argon gas again by oil pump, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, simultaneously when reaction system adds 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, with temperature is that 30-70 ℃ methyl alcohol and deionized water washes this black solid respectively twice, in vacuum dry 10-30 minute, obtain above-mentioned 3,6-dithienyl-pyrrolopyrrole diketone, this step 3, the productive rate of 6-dithienyl-pyrrolopyrrole diketone 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-pyrrolopyrrole diketone
In reactor, vacuumize by oil pump, feed nitrogen again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, when reaction system adds reactant, also keep this protection of nitrogen gas simultaneously.
With 3 of 43.3mmol, 6-dithienyl-pyrrolopyrrole diketone 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, be that leacheate carries out silica gel column chromatography to dry thing again with the methylene dichloride, obtain above-mentioned 2,5-dioctyl-3,6-dithienyl-pyrrolopyrrole diketone, this step 2,5-dioctyl-3, the productive rate of 6-dithienyl-pyrrolopyrrole diketone 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-pyrrolopyrrole diketone
In reactor, vacuumize by oil pump, feed argon gas again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, simultaneously when reaction system adds reactant, the protection that also keeps this argon gas.
With 2 of 8.6mmol, 5-dioctyl-3, the N-bromo-succinimide of 6-dithienyl-pyrrolopyrrole diketone 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, 30 minutes after-filtration are collected and are leached thing, with 50 ℃ washed with methanol 2 times, vacuum-drying 10-30 minute, be that leacheate carries out the silica gel column chromatography separation to dried reactant again with the methylene dichloride, obtain above-mentioned 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone, this step 2,5-dioctyl-3, the productive rate of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone 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, feed nitrogen again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, when reaction system adds reactant, also keep this protection of nitrogen gas simultaneously.
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-pyrrolopyrrole diketone, 0.02mmol tetra-triphenylphosphine palladium, the sodium carbonate solution of the 2mol/L of 10mL, the 30mL methylbenzene is put in the reactor, reacts 72 hours down at 90 ℃.
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, be leacheate with the methylene dichloride, 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, preparation 9, the basic anthracene of 10-two (4,4,5,5 ,-tetramethyl--1,3,2-two assorted oxygen pentaboranes)
9, the preparation process of the basic anthracene of 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-pyrrolopyrrole diketone
Put up the anhydrous and oxygen-free reaction unit, vacuumize, feed argon gas again by oil pump, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, simultaneously when reaction system adds reactant, the protection that also keeps this argon gas.
In reactor, the potassium tert.-butoxide that adds 22mmol, 4-hexyloxy-2-cyano thiophene of 20.0mmol 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, with temperature is that 30-70 ℃ methyl alcohol and deionized water washes this black solid respectively twice, in vacuum dry 10-30 minute, obtain above-mentioned 3,6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone, this step 3, the productive rate of 6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone 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-pyrrolopyrrole diketone
In reactor, vacuumize by oil pump, feed argon gas again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, simultaneously when reaction system adds reactant, the protection that also keeps this argon gas.
With 3 of 43.3mmol, 6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone 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, be that leacheate carries out silica gel column chromatography to dry thing again with the methylene dichloride, obtain above-mentioned 2,5-dioctyl-3,6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone, this step 2,5-dioctyl-3, the productive rate of 6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone 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-pyrrolopyrrole diketone
In reactor, vacuumize by oil pump, feed nitrogen again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, when reaction system adds reactant, also keep this protection of nitrogen gas simultaneously.
With 2 of 5mmol, 5-dioctyl-3, the N-bromo-succinimide of 6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone and 14mmol is dissolved in the chloroform of 250mL, constantly stirs, in 10-40 ℃ of following lucifuge reaction 30 hours.
Reaction liquid after the reaction end is poured in the methanol solution of 250mL, 30 minutes after-filtration are collected and are leached thing, with 50 ℃ washed with methanol 2 times, vacuum-drying 10-30 minute, to be leacheate again with the methylene dichloride carry out silica gel column chromatography to dried reactant separates, obtain above-mentioned 2,5-dioctyl-3,6-two (5-bromo-4 hexyloxy thiophene) base-pyrrolopyrrole diketone, the reaction formula of this step 4 is expressed as:
The preparation of step 5, organic copolymer P2
In reactor, vacuumize by oil pump, feed argon gas again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, simultaneously when reaction system adds 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-pyrrolopyrrole diketone, 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, be leacheate with the methylene dichloride, 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, feed nitrogen again by oil pump, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of nitrogen gas, when reaction system adds reactant, also keep this protection of nitrogen gas simultaneously.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, feed nitrogen again by oil pump, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of nitrogen gas, when reaction system adds reactant, also keep this protection of nitrogen gas simultaneously.
With 9 of 5.0mmol, 10-two bromo-2, (the synthetic method of this compound is referring to 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 steam 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-pyrrolopyrrole diketone
3, the preparation process of 6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone is as described in embodiment 2 step 2.
Step 3,2,5-dioctyl-3, the preparation of 6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone
2,5-dioctyl-3, the preparation process of 6-two (4-hexyloxy) thienyl-pyrrolopyrrole diketone 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-pyrrolopyrrole diketone
2,5-dioctyl-3, the preparation process of 6-two (5-bromo-4 hexyloxy thiophene) base-pyrrolopyrrole diketone is as described in embodiment 2 step 4.
The preparation of step 5, organic copolymer P1
In reactor, vacuumize by oil pump, feed nitrogen again, 3-4 time so repeatedly, feed nitrogen more always reaction system is under the protection of argon gas, when reaction system adds reactant, also keep this protection of nitrogen gas simultaneously.
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-pyrrolopyrrole diketone, the tetra-triphenylphosphine palladium of 0.01mmol, the sodium carbonate solution of the 2mol/L of 8mL, the 40mL methylbenzene is put in the reactor, reacts 48 hours down at 85 ℃.
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, be leacheate with the methylene dichloride, 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 material without limits, still 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, the 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 an integral unit, is also referred to as ito glass, can buy from the market.
Above-mentioned organic solar batteries preparation of devices method is as follows,
Is 1 with organic copolymer P1 and PCBM with weight ratio: 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 vacuum deposition method again, 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, reduce to room temperature again, 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 the 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 material without limits, 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 on 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 the octadecyl trichlorosilane 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 restriction the present invention, all any modifications of being done 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 pyrrolopyrrole derovatives that provides anthracene derivant that following structure formula II represents and structure formula III to represent respectively;
Under the oxygen free condition, the pyrrolopyrrole derovatives that anthracene derivant that following structure formula II is represented and structure formula III are represented 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 is represented, 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 pyrrolopyrrole derovatives is 1: 1 to 1: 4; The 0.5%-10% of the molar weight of the anthracene derivant that the molar weight of described catalyzer is represented for the 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 is represented:
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 is represented, 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 is represented and the mol ratio of lithium alkylide are 1.0: 2.0 to 1.0: 4.0; Anthracene derivant that described structure formula IV is represented and lithium alkylide reaction added two tetramethyl ethylene ketones again and close two boron after 1-8 hour; The 2.0-4.0 of the anthracene derivant molar weight that the molar weight that the described pair of tetramethyl ethylene ketone closes two boron is represented for the structure formula IV doubly.
7. organic copolymer preparation method as claimed in claim 3 is characterized in that, also comprises the preparation method of the pyrrolopyrrole derovatives that the structure formula III is represented:
Under the oxygen free condition, the 2-cyano thiophene derivative that to be represented by structural formula (V) and structure formula VI respectively is dissolved in the organic solvent, in alkaline agent, temperature is under the 90-120 ℃ of condition, add dimethyl succinate reaction 1-4 hour, obtain the derivative of the pyrrolopyrrole diketone of structural formula (VII) expression, the reaction formula of this step is expressed as:
Under the oxygen free condition, the pyrrolopyrrole derovatives of said structure formula (VII) expression is dissolved in the organic solvent, in alkaline agent, temperature is under the 120-150 ℃ of condition, add the bromine substituent of representing by following structural formula (VIII) and structural formula (IX) respectively, reacted 10-22 hour, obtain the pyrrolopyrrole derovatives of structural formula (X) expression, the reaction formula of this step is expressed as:
Under the condition of anaerobic, the pyrrolopyrrole derovatives 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 pyrrolopyrrole derovatives that the said structure formula III is represented, 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 described 2-cyano thiophene integral molar quantity of being represented by structural formula (V) and structure formula VI respectively and dimethyl succinate is 2-4: 1; After described 2-cyano thiophene of representing by structural formula (V) and structure formula VI respectively and the dimethyl succinate reaction,, continue reaction 1-5 hour with the reaction liquid distillation; In the derivative preparation method of the pyrrolopyrrole diketone of described structural formula (VII) expression, the molar weight of alkaline agent neutral and alkali thing is 1-2 a times of the 2-cyano thiophene integral molar quantity represented 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 pyrrolopyrrole diketone of structural formula (VII) is 2-3 with the ratio of the mole total amount of the substituent of the bromine of being represented by structural formula (VIII) and structural formula (IX) respectively: 1; The pyrrolopyrrole derovatives 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010190118 CN102260371B (en) | 2010-05-27 | 2010-05-27 | Organic copolymer, its preparation method and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010190118 CN102260371B (en) | 2010-05-27 | 2010-05-27 | Organic copolymer, its preparation method and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102260371A true CN102260371A (en) | 2011-11-30 |
| CN102260371B CN102260371B (en) | 2013-04-24 |
Family
ID=45007228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010190118 Expired - Fee Related CN102260371B (en) | 2010-05-27 | 2010-05-27 | Organic copolymer, its preparation method and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102260371B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848968A (en) * | 2012-11-28 | 2014-06-11 | 海洋王照明科技股份有限公司 | Polymer containing thienopyrrole dione-dibenzothiophene benzodithiophene, preparation method and application thereof |
| CN103865038A (en) * | 2012-12-12 | 2014-06-18 | 海洋王照明科技股份有限公司 | Conjugated polymer containing diketopyrrolopyrrole-dibenzothiophenebenzodithiophene and preparation method and application thereof |
| 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 |
| CN105742501A (en) * | 2016-05-03 | 2016-07-06 | 苏州大学 | Organic electric memory device based on phosphonic acid or trichlorosilane-modified ITO glass substrate and preparation method for organic electric memory device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1977029A (en) * | 2004-06-29 | 2007-06-06 | 西巴特殊化学品控股有限公司 | Fluorescent quinacridones |
| WO2009047104A2 (en) * | 2007-10-09 | 2009-04-16 | Basf Se | Pyrrolopyrrole derivatives, their manufacture and use |
| CN101654517A (en) * | 2008-08-18 | 2010-02-24 | 施乐公司 | Semiconducting polymers |
-
2010
- 2010-05-27 CN CN 201010190118 patent/CN102260371B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1977029A (en) * | 2004-06-29 | 2007-06-06 | 西巴特殊化学品控股有限公司 | Fluorescent quinacridones |
| WO2009047104A2 (en) * | 2007-10-09 | 2009-04-16 | Basf Se | Pyrrolopyrrole derivatives, their manufacture and use |
| CN101654517A (en) * | 2008-08-18 | 2010-02-24 | 施乐公司 | Semiconducting polymers |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103848968A (en) * | 2012-11-28 | 2014-06-11 | 海洋王照明科技股份有限公司 | Polymer containing thienopyrrole dione-dibenzothiophene benzodithiophene, preparation method and application thereof |
| CN103848968B (en) * | 2012-11-28 | 2016-04-20 | 海洋王照明科技股份有限公司 | A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer and preparation and application thereof |
| CN103865038A (en) * | 2012-12-12 | 2014-06-18 | 海洋王照明科技股份有限公司 | Conjugated polymer containing diketopyrrolopyrrole-dibenzothiophenebenzodithiophene and preparation method and application thereof |
| CN103865038B (en) * | 2012-12-12 | 2016-02-10 | 海洋王照明科技股份有限公司 | Containing the conjugated polymers and its preparation method and application of pyrrolo-pyrrole-dione-dibenzothiophene benzene 1,4-Dithiapentalene |
| 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 |
| CN105742501A (en) * | 2016-05-03 | 2016-07-06 | 苏州大学 | Organic electric memory device based on phosphonic acid or trichlorosilane-modified ITO glass substrate and preparation method for organic electric memory device |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102260371B (en) | 2013-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102906152B (en) | Polymer containing units of fluorene, anthracene and benzothiadiazole, preparation method and uses thereof | |
| CN102050940B (en) | Organic semiconductor material containing 6-R group- [1, 2, 5] thiazole [3, 4-g] benzotriazole and application thereof | |
| CN102295749B (en) | Fluorine copolymer containing thiophene and pyrrole-pyrrole units and preparation method as well as application thereof | |
| CN102276803B (en) | Polymeric material containing anthracene and pyrrole-pyrrole-dione unit, preparation method thereof and application thereof | |
| CN102686592B (en) | Copolymer containing fluorenylporphyrin-anthracene, preparation method and use thereof | |
| EP2562197A1 (en) | Copolymer comprising anthracene and benzoselenadiazole, preparing method and uses thereof | |
| CN101787020A (en) | Organic conjugated molecule capable of being processed by solution and application thereof in solar cells | |
| CN102260371B (en) | Organic copolymer, its preparation method and its application | |
| CN101962380B (en) | Novel organic conjugated molecule and application thereof in organic solar cell | |
| CN102453228B (en) | Organic semiconductor material containing fluorene, anthracene and benzodithiophene units, preparation method, and application thereof | |
| CN102712652B (en) | Copolymer containing fluorenylporphyrin-benzene, preparation method and use thereof | |
| CN102286141B (en) | Organic semiconductor material containing fluorene, anthracene and thiophene bithiophene, preparation method thereof and application thereof | |
| CN102295748B (en) | Fluorine polymer containing anthracene and pyrrole-pyrrole-dione units and preparation method and use thereof | |
| CN103080183B (en) | Fluorene containing organic semiconductor material, preparation method and use thereof | |
| CN102146153A (en) | Perylene tetracarboxylic diimide-carbazole-dithienyldiazosulfide conjugated polymer as well as preparation method and application thereof | |
| CN102477143B (en) | Fluorene-containing organic semiconductor material, and preparation method and application thereof | |
| CN102311535B (en) | Polymer containing fluorene, anthracene and thienopyrazine units and preparation method as well as application thereof | |
| CN102161750B (en) | Anthracene-diazosulfide copolymer, and preparation method and application thereof | |
| CN102372838B (en) | Organic semiconductor material based on fluorene, anthracene and quinoxaline, preparation method thereof and application thereof | |
| CN102268128B (en) | Porphyrin copolymer containing thienophenazine unit as well as preparation method and application thereof | |
| CN102206330B (en) | Bi-thiophene silole-containing conjugated polymer and preparation method and application thereof | |
| CN102146152B (en) | Anthracene thiophene-contained copolymer as well as preparation method and application thereof | |
| CN102372841B (en) | Copolymer containing fluorine units, anthracene units and quinoxaline units, preparation method, and application thereof | |
| CN102443142B (en) | Fluorene, anthracene and 2-thiophene thiazide-containing copolymer and preparation method and application thereof | |
| CN103154002B (en) | Organic semiconductor material, preparation methods and uses thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130424 Termination date: 20190527 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |