CN103665339A - Diketopyrrolopyrrole-base polymer, and preparation method and application thereof - Google Patents
Diketopyrrolopyrrole-base polymer, and preparation method and application thereof Download PDFInfo
- Publication number
- CN103665339A CN103665339A CN201210346665.9A CN201210346665A CN103665339A CN 103665339 A CN103665339 A CN 103665339A CN 201210346665 A CN201210346665 A CN 201210346665A CN 103665339 A CN103665339 A CN 103665339A
- Authority
- CN
- China
- Prior art keywords
- pyrrolo
- pyrrole
- based polyalcohol
- preparation
- dione based
- 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.)
- Pending
Links
- 0 *c(cc1)ccc1N(c1ccc(C=C)cc1)c1ccc(C=C)cc1 Chemical compound *c(cc1)ccc1N(c1ccc(C=C)cc1)c1ccc(C=C)cc1 0.000 description 2
- JWLQXFRKQGNWBV-SREVYHEPSA-N CC(C)(C)/C(/NC)=C/C Chemical compound CC(C)(C)/C(/NC)=C/C JWLQXFRKQGNWBV-SREVYHEPSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention belongs to the field of solar cell materials, and discloses a diketopyrrolopyrrole-base polymer which has the following structural formula, wherein R1 and R2 are respectively a C1-C20 alkyl group, and n is a whole number ranging from 10 to 50. In the diketopyrrolopyrrole-base copolymer, the DPP has the advantages of high absorptivity, high photochemical stability and the like; the DPP can modify the alkyl chain through N atoms; when the lengths of thiophenes connected to the 3 site and 6 site of the DPP are increased, the absorption range becomes wider, and the band gap becomes smaller; and all of the properties can enhance the energy conversion efficiency of the organic solar cell.
Description
Technical field
The present invention relates to solar cell material field, relate in particular to a kind of pyrrolo-pyrrole-dione based polyalcohol and preparation method thereof.The invention still further relates to the application of pyrrolo-pyrrole-dione based polyalcohol in organic solar batteries.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.The current silicon wafer battery for ground, because complex manufacturing, cost are high, is restricted its application.In order to reduce battery cost, expand range of application, people are finding novel solar cell material always for a long time.Organic semiconductor material with its raw material be easy to get, cheap, preparation technology is simple, environmental stability good, have the good advantages such as photovoltaic effect to receive much concern.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C
60between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed, but still much lower than the efficiency of conversion of inorganic solar cell.The main restricting factor that limiting performance improves has: the spectral response of organic semiconductor material is not mated with solar radiation spectrum, the electrode collection effciency of the carrier mobility that organic semiconductor is relatively low and lower current carrier etc.For polymer solar battery is on the actual application, the material of development of new, and then increase substantially the top priority that its effciency of energy transfer is still this research field.
Pyrrolo-pyrrole-dione (DPP) has the advantages such as absorption is strong, photochemical stability, very potential being applied in organic solar batteries.DPP can be by carrying out the modification of alkyl chain on N atom, and when increase is connected to the length of the thiophene of 3,6 of DPP, absorption region broadens, and band gap also diminishes simultaneously, and these character are strong for the raising of solar cell transformation efficiency.
Summary of the invention
Problem to be solved by this invention is to provide a kind of pyrrolo-pyrrole-dione based polyalcohol that can improve organic solar batteries energy conversion efficiency.
Technical scheme of the present invention is as follows:
A pyrrolo-pyrrole-dione based polyalcohol, has following structural formula:
In formula, R
1, R
2be C
1～C
20alkyl, the integer that n is 10-50.
In this polymkeric substance,, R
1, R
2can be identical, can be not identical yet.
The present invention also provides the preparation method of above-mentioned pyrrolo-pyrrole-dione based polyalcohol, comprises the steps:
The compd A and the B that provide respectively following structural formula to represent,
Under oxygen-free environment, compd A and B are added into the organic solvent that contains catalyzer according to the ratio of mol ratio 1:1～1.2, after dissolving, under 70～130 ° of C, carry out Heck coupling reaction 24～96 hours, after cooling, stop polyreaction, obtain the described pyrrolo-pyrrole-dione based polyalcohol that following structural formula represents:
Above-mentioned various in, R
1, R
2be C
1～C
20alkyl, the integer that n is 10-50.
In the preparation method of described pyrrolo-pyrrole-dione based polyalcohol:
Described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium; Or
Described catalyzer is the mixture of organic palladium and organophosphorus ligand; The mol ratio of described organic palladium and organophosphorus ligand is 1:4～8; Described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Described organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl; The mixture that organic palladium and organophosphorus ligand form can be palladium and tri-o-tolyl phosphine mixture or three or two argon benzyl acetone two palladiums and 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl mixture;
In coupling reaction, the mol ratio of catalyzer and compd A is 1:20 ~ 1:100;
Organic solvent is at least one in toluene, DMF and tetrahydrofuran (THF).
In the preparation method of pyrrolo-pyrrole-dione based polyalcohol, in oxygen-free environment, gas comprises at least one in nitrogen and rare gas element, preferred nitrogen.
The preparation method of described pyrrolo-pyrrole-dione based polyalcohol, preferably, described Heck coupling reaction temperature is 90～120 ° ' the C reaction times is 24～96 hours.
In the preparation method of described pyrrolo-pyrrole-dione based polyalcohol, the pyrrolo-pyrrole-dione based polyalcohol making is mixture, also need it to carry out purification processes, as:
After Heck coupling reaction stops, to dripping in the mixed solution that obtains after reaction, in methyl alcohol, carry out sedimentation, after filtering by apparatus,Soxhlet's subsequently, use successively methyl alcohol and normal hexane extracting 24h, then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for the pyrrolo-pyrrole-dione based polyalcohol that obtains purifying.
This law also provides the application of above-mentioned pyrrolo-pyrrole-dione based polyalcohol in the active coating of organic solar batteries.
In pyrrolo-pyrrole-dione based polyalcohol of the present invention, pyrrolo-pyrrole-dione (DPP) has the advantages such as absorption is strong, photochemical stability, DPP can carry out by N atom the modification of alkyl chain, when increase is connected to 3 of DPP and 6 s' the length of thiophene, absorption region broadens, simultaneously band gap also diminishes etc.,, these character can improve the energy conversion efficiency of organic solar batteries.Thiodiphenylamine is the class nitrogen that contains electron rich and the heteroaromatic compound of sulphur atom, has good cavity transmission ability, and N is upper by alkyl modified, thereby improves solubility property and the film forming properties of multipolymer.
Separately, the preparation method of above-mentioned pyrrolo-pyrrole-dione based polyalcohol, has adopted better simply synthetic route, thereby reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And worth polymeric material novel structure, solubility property is good, and film forming properties is good, applicable to organic solar batteries.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of the pyrrolo-pyrrole-dione based polyalcohol that makes of embodiment 1;
Fig. 2 is the structural representation of the organic solar batteries that makes of embodiment 6.
Embodiment
Below in conjunction with accompanying drawing, preferred embodiment of the present invention is described in further detail.
In order to understand better content of the present invention, below by concrete example and legend, further illustrate technology case of the present invention, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein the monomer of compd A is bought and is obtained from the market, monomer reference literature (Adv.Funct.Mater., 2009 of compd B, 19,3063) disclosed method is synthetic obtains.
Embodiment 1
The pyrrolo-pyrrole-dione based polyalcohol of the present embodiment, gather { 4,4'-divinyl-N-(4-octane oxygen base phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-di-n-octyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone }, wherein, R1 is octane base, and R2 is octane base, n=15; Its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under argon shield, 4,4'-divinyl-N-(4-octane oxygen base phenyl) pentanoic (85mg, 0.2mmol), 3, two (the bromo-2-thienyls of 5-)-2 of 6-, 5-dihydro-2,5-di-n-octyl pyrrolo-[3,4-c] pyrroles-1,4-diketone (136.4mg, 0.2mmol) adds in the flask that fills 10ml toluene solvant, vacuumizes deoxygenation and is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol); Flask is heated to 100 ℃ and carries out Heck coupling reaction 60h.Subsequently, after cooling, stop polyreaction, to dripping in flask, in 50ml methyl alcohol, carry out sedimentation; After filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, under vacuum pump, taking out spends the night obtains poly-{ 4,4'-divinyl-N-(the 4-octane oxygen base phenyl) pentanoic-co-3 of purified product, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-di-n-octyl pyrrolo-[3,4-c] pyrroles-1,4-diketone }, productive rate 65%. test results are: Molecular weight (GPC, THF, R.I): M
n=23.3kDa, M
w/ M
n=2.2.
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of the pyrrolo-pyrrole-dione based polyalcohol that makes of embodiment 1.
As shown in Figure 1, pyrrolo-pyrrole-dione based polyalcohol has large wider absorption between 350nm ~ 700nm, and wherein maximum absorption band is positioned at 618nm left and right.
Embodiment 2:
The pyrrolo-pyrrole-dione based polyalcohol of the present embodiment, gather { 4,4'-divinyl-N-(4-p-methoxy-phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-di-n-octyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone }, wherein, R1 is methyl, and R2 is NSC 62789 base, n=12; Its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 4, 4'-divinyl-N-(4-p-methoxy-phenyl) pentanoic (98mg, 0.3mmol), 3, two (the bromo-2-thienyls of 5-)-2 of 6-, 5-dihydro-2, 5-bis-NSC 62789 base pyrrolo-es [3, 4-c] pyrroles-1, 4-diketone (306mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 70 ℃ and carry out Heck coupling reaction 96h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain purified product poly-{ 4,4'-divinyl-N-(4-p-methoxy-phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-di-n-octyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone }.Productive rate is 68%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=20.7kDa, M
w/ M
n=2.3.
Embodiment 3:
The pyrrolo-pyrrole-dione based polyalcohol of the present embodiment, gather { 4,4'-divinyl-N-(4-NSC 62789 oxygen base phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-dimethyl pyrrole is [3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone also }, wherein, R1 is NSC 62789 base, and R2 is methyl, n=50; Its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 4,4'-divinyl-N-(4-NSC 62789 oxygen base phenyl) pentanoic (178mg, 0.3mmol), 3, two (the bromo-2-thienyls of 5-)-2 of 6-, 5-dihydro-2,5-diformazan alkyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone (160.4mg, 0.33mmol), palladium (3.5mg, 0.015mmol) He three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) join in the flask of the DMF that fills 12mL, in flask, lead to after the about 20min of nitrogen purge gas subsequently; Flask is heated to 130 ℃ and carries out Heck coupling reaction 24h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, obtain poly-{ 4,4'-divinyl-N-(the 4-NSC 62789 oxygen base phenyl) pentanoic-co-3 of purified product, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-dimethyl pyrrole is [3,4-c] pyrroles-1 also, 4-diketone }, productive rate is 72%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=41.9kDa, M
w/ M
n=2.0.
Embodiment 4:
The pyrrolo-pyrrole-dione based polyalcohol of the present embodiment, gather { 4,4'-divinyl-N-(2-bis-normal butane oxygen base phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-bis-positive decyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone }, wherein, R1 is normal-butyl, and R2 is positive decyl, n=36; Its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 4,4'-divinyl-N-(2-bis-normal butane oxygen base phenyl) pentanoic (111mg, 0.3mmol), 3, two (the bromo-2-thienyls of 5-)-2 of 6-, 5-dihydro-2,5-bis-n-decane base pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone (266mg, 0.36mmol), three or two argon benzyl acetone two palladium (9mg, 0.009mmol), with 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) joins the N that fills 12mL, in the flask of dinethylformamide, in flask, lead to after the about 20min of nitrogen purge gas subsequently; Flask is heated to 120 ℃ and carries out Heck coupling reaction 36h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h; Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection, under vacuum, after 50 ℃ of dry 24h, obtain poly-{ 4,4'-divinyl-N-(the 2-bis-normal butane oxygen base phenyl) pentanoic-co-3 of purified product, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-bis-positive decyl pyrrolo-[3,4-c] pyrroles-1,4-diketone }, productive rate is 75%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=33.5kDa, M
w/ M
n=2.2.
Embodiment 5:
The pyrrolo-pyrrole-dione based polyalcohol of the present embodiment, gather { 4,4'-divinyl-N-(2-bis-n-dodecane oxygen base phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-di-n-hexyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone }, wherein, R1 is dodecyl, and R2 is n-hexyl, n=10; Its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and the protection of argon gas gas mixture, by 4, 4'-divinyl-N-(2-bis-n-dodecane oxygen base phenyl) pentanoic (145mg, 0.3mmol), 3, two (the bromo-2-thienyls of 5-)-2 of 6-, 5-dihydro-2, 5-di-n-hexyl pyrrolo-[3, 4-c] pyrroles-1, 4-diketone (188mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after fully dissolving, pass into after the about 20min of gas mixture air-discharging of nitrogen and argon gas, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, again after the about 10min of gas mixture air-discharging of fully logical nitrogen and argon gas, two-mouth bottle is joined to 90 ℃ and carry out Heck coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after filtering by apparatus,Soxhlet's, use successively methyl alcohol and normal hexane extracting 24h.Then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, under vacuum, after 50 ℃ of dry 24h, obtain purified product poly-{ 4,4'-divinyl-N-(2-bis-n-dodecane oxygen base phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-di-n-hexyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone }.Productive rate is 60%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=18.3kDa, M
w/ M
n=2.3.
Embodiment 6
The present embodiment is organic solar batteries, the electron donor material of its active coating is the pyrrolo-pyrrole-dione based polyalcohol that embodiment 1 makes, gather { 4,4'-divinyl-N-(4-octane oxygen base phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-di-n-octyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone } (with P1, representing).
Refer to Fig. 2, this organic solar batteries 60 comprises substrate 61, anode layer 62, buffer layer 63, active coating 64 and the negative electrode 65 stacking gradually.
The preparation technology of the organic solar batteries of the present embodiment is as follows:
Use successively sanitising agent, deionized water, ethanol, acetone ultrasonic cleaning substrate 61, substrate 61 is glass;
A side at substrate 61 prepares by magnetron sputtering the anode layer 62 that a layer thickness is 140nm, uses successively subsequently sanitising agent, deionized water, ethanol, acetone ultrasonic cleaning, and processes with oxygen-Plasma; In the present embodiment, anode layer 62 is ITO(tin indium oxide), preferably, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth;
The buffer layer 63 that plays modification that is 100nm in anode layer 62 surface-coated a layer thickness; The material of buffer layer 63, for poly-3,4-Ethylenedioxy Thiophene (PEDOT) and polystyrene-sulfonic acid (PSS) matrix material, is expressed as PEDOT:PSS;
The active coating 64 that is 160nm in buffer layer 63 surface-coated a layer thickness; The material of active coating 64 comprises electron donor material and electron acceptor material, and the mol ratio of electron donor material and electron acceptor material is 1:2; Wherein, electron acceptor material is (6,6) phenyl-C
61-methyl-butyrate (PCBM), electron donor material be the present embodiment 1 make poly-{ 4,4'-divinyl-N-(4-octane oxygen base phenyl) pentanoic-co-3, two (the 5-base-2-thienyls)-2 of 6-, 5-dihydro-2,5-di-n-octyl pyrrolo-[3,4-c] pyrroles-Isosorbide-5-Nitrae-diketone } (P1).
The cathode layer 65 that is 80nm in active coating 64 surface vacuum evaporation a layer thickness; Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc.In the present embodiment, the material of cathode layer 65 is aluminium.
Above-mentioned organic solar energy cell structure is: i.e. glass/ITO/PEDOT:PSS/PCBM:P1/Al.
Be appreciated that buffer layer 63 also can omit, now active coating 64 is directly formed at anode layer 62 surfaces.
In the present embodiment, this organic solar batteries device 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to again room temperature, after solar cell device is annealed, can effectively increase order and the regularity between interior each group of molecule and molecule segment, arranged, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
At AM1.5; 100mW/cm
2under illumination, the effciency of energy transfer 3.5% of the body heterojunction solar cell that the multipolymer based in embodiment 1 is donor material.
When this solar cell device 60 is used, under illumination, light transmission substrate 61 and anode layer 62, the conduction hole type electroluminescent material in active coating 64 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to cathode layer 65, transmit and be collected by negative electrode, transmit and collected by anode layer 62 along electron donor material anode layer 62 in hole freely, thereby form photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In this process, conduction hole type electroluminescent material, because it has very wide spectral response range, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, be convenient to large batch of preparation.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. a pyrrolo-pyrrole-dione based polyalcohol, is characterized in that, has following structural formula:
In formula, R
1, R
2be C
1～C
20alkyl, the integer that n is 10-50.
2. a preparation method for pyrrolo-pyrrole-dione based polyalcohol, is characterized in that, comprises the steps:
The compd A and the B that provide respectively following structural formula to represent,
Under oxygen-free environment, compd A and B are added into the organic solvent that contains catalyzer according to the ratio of mol ratio 1:1～1.2, after dissolving, under 70～130 ° of C, carry out Heck coupling reaction 24～96 hours, after cooling, stop polyreaction, obtain the described pyrrolo-pyrrole-dione based polyalcohol that following structural formula represents:
Above-mentioned various in, R
1, R
2be C
1～C
20alkyl, the integer that n is 10-50.
3. the preparation method of pyrrolo-pyrrole-dione based polyalcohol according to claim 2, is characterized in that, described catalyzer is bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium.
4. the preparation method of pyrrolo-pyrrole-dione based polyalcohol according to claim 2, is characterized in that, described catalyzer is the mixture of organic palladium and organophosphorus ligand; The mol ratio of described organic palladium and organophosphorus ligand is 1:4～8.
5. the preparation method of pyrrolo-pyrrole-dione based polyalcohol according to claim 5, is characterized in that, described organic palladium is palladium or three or two argon benzyl acetone two palladiums; Described organophosphorus ligand is tri-o-tolyl phosphine or 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl.
6. according to the preparation method of the pyrrolo-pyrrole-dione based polyalcohol described in claim 2,3 or 4, it is characterized in that, the mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
7. the preparation method of pyrrolo-pyrrole-dione based polyalcohol according to claim 2, is characterized in that, described Heck coupling reaction temperature is 90～120 ° ' the C reaction times is 24～96 hours.
8. the preparation method of pyrrolo-pyrrole-dione based polyalcohol according to claim 2, is characterized in that, described organic solvent is at least one in toluene, DMF and tetrahydrofuran (THF).
9. the preparation method of pyrrolo-pyrrole-dione based polyalcohol according to claim 2, is characterized in that, after Heck coupling reaction stops, also needing pyrrolo-pyrrole-dione based polyalcohol to carry out purification process:
After Heck coupling reaction stops, to dripping in the mixed solution that obtains after reaction, in methyl alcohol, carry out sedimentation, after filtering by apparatus,Soxhlet's subsequently, use successively methyl alcohol and normal hexane extracting 24h, then take chloroform as solvent extraction is to colourless, collect chloroformic solution and be spin-dried for the pyrrolo-pyrrole-dione based polyalcohol that obtains purifying.
10. a pyrrolo-pyrrole-dione based polyalcohol claimed in claim 1 application in the active coating of organic solar batteries.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210346665.9A CN103665339A (en) | 2012-09-18 | 2012-09-18 | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210346665.9A CN103665339A (en) | 2012-09-18 | 2012-09-18 | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103665339A true CN103665339A (en) | 2014-03-26 |
Family
ID=50304188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210346665.9A Pending CN103665339A (en) | 2012-09-18 | 2012-09-18 | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103665339A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727570A (en) * | 2018-06-11 | 2018-11-02 | 黑龙江大学 | A kind of DPP block polymers, preparation method and application containing trianilino group |
| CN108727569A (en) * | 2018-06-11 | 2018-11-02 | 黑龙江大学 | A kind of DPP block polymers, preparation method and the application of carbazolyl-containing group |
| CN108976413A (en) * | 2018-06-11 | 2018-12-11 | 黑龙江大学 | A kind of DPP block polymer, preparation method and the application of the trianilino group containing phenyl |
-
2012
- 2012-09-18 CN CN201210346665.9A patent/CN103665339A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727570A (en) * | 2018-06-11 | 2018-11-02 | 黑龙江大学 | A kind of DPP block polymers, preparation method and application containing trianilino group |
| CN108727569A (en) * | 2018-06-11 | 2018-11-02 | 黑龙江大学 | A kind of DPP block polymers, preparation method and the application of carbazolyl-containing group |
| CN108976413A (en) * | 2018-06-11 | 2018-12-11 | 黑龙江大学 | A kind of DPP block polymer, preparation method and the application of the trianilino group containing phenyl |
| CN108976413B (en) * | 2018-06-11 | 2020-10-02 | 黑龙江大学 | DPP (dipeptidyl peptidase) block polymer containing phenyltriphenylamine group as well as preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103965445A (en) | Polymer containing dithiophen benzothiadiazole unit and preparation method thereof, and solar cell device | |
| CN103848977A (en) | Dithienyldiazosulfide unit-containing polymer, preparation method thereof and solar cell device | |
| CN103665339A (en) | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof | |
| CN104513370A (en) | Diketopyrrolo pyrrole based copolymer, preparation method, and applications thereof | |
| CN104017187A (en) | Isoindigo group-containing polymer as well as preparation method and application thereof | |
| CN104177600A (en) | Polymer containing dithiazolebenzothiadiazole group, preparation method and organic solar cell device thereof | |
| CN103626963A (en) | Diketopyrrolopyrrole unit-containing polymer, preparation method of diketopyrrolopyrrole unit-containing polymer and solar cell device | |
| CN103665338A (en) | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof | |
| CN103897155A (en) | Thienothiophene unit-containing polymer and preparation method thereof and solar energy cell device | |
| CN103897150B (en) | Containing polymkeric substance and preparation method thereof and the solar cell device of thienothiophene unit | |
| CN104017182A (en) | Benzothiadiazolyl containing polymer and preparation method and application thereof | |
| CN103848965A (en) | Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device | |
| CN103665340A (en) | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof | |
| CN103665341A (en) | Diketopyrrolopyrrole-base polymer, and preparation method and application thereof | |
| CN103804644A (en) | Benzothiazolyl copolymer as well as preparation method and application thereof | |
| CN103665336A (en) | Benzothiazole-containing unit polymer, preparation method and application thereof | |
| CN104119512A (en) | Polymer containing difluoro diazosulfide unit and preparation method thereof and solar cell device | |
| CN103848970A (en) | Polymer containing bithiophene diazosulfide unit, its preparation method and solar cell device | |
| CN103848972A (en) | Polymer containing bithiophene diazosulfide unit, its preparation method and solar cell device | |
| CN103848964A (en) | Polymer containing thiophene-benzene-thiophene unit and preparation method thereof, and solar cell device | |
| CN103897147A (en) | Polymer containing bithiazole units, preparation method thereof, and solar cell device | |
| CN103665337A (en) | Pyrrolopyrrolidone copolymer as well as preparation method and application thereof | |
| CN104017178A (en) | Polymer containing diketopyrrolopyrrole group as well as preparation method and application thereof | |
| CN104177594A (en) | Benzo dithienyl-containing polymer and preparation method thereof and organic solar energy cell device | |
| CN104017175A (en) | Thienothienyl containing polymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140326 |