CN102070776B - Preparation method and film forming method of segmented copolymers with fullerene at main chain - Google Patents
Preparation method and film forming method of segmented copolymers with fullerene at main chain Download PDFInfo
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- CN102070776B CN102070776B CN 201010577889 CN201010577889A CN102070776B CN 102070776 B CN102070776 B CN 102070776B CN 201010577889 CN201010577889 CN 201010577889 CN 201010577889 A CN201010577889 A CN 201010577889A CN 102070776 B CN102070776 B CN 102070776B
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Abstract
The invention belongs to the technical field of organic photovoltaic materials, in particular to a preparation method and a film forming method of segmented copolymers with fullerene at a main chain. The segmented copolymers consist of fullerene, polyalkoxylated thiofuran and polylactic acid, and the segmented copolymers can automatically form micro-phase separation structures under the controllable dimension in the film forming process, so electron hole pairs are effectively separated on a micro-phase interface, the micro-phase separation structures formed by the method have good stability, the fullerene is used as electron receiving materials to be sequentially arranged on the micro-phase interface, and the consumption of the expensive fullerene is greatly saved. The preparation method provided by the invention has the advantages of simple and convenient process, high film forming quality, high input-output ratio, low cost, wide application prospects and the like. Products prepared by using the preparation method provided by the invention belong to a new generation of green environmental-protection high-performance chemical engineering products and can be used in the field of organic photovoltaic materials.
Description
Technical field
The invention belongs to organic photovoltaic material technology field, be specifically related to preparation method and film thereof that a kind of main chain contains the segmented copolymer of soccerballene.
Background technology
Along with exhausting day by day of development of modern industry and fossil energy, energy demand becomes the focus that countries in the world are paid close attention to.Develop various new forms of energy, development light weight, inexpensive, power supply that thing is beautiful become the target that scientist seek assiduously.As everyone knows, sun power is inexhaustible.But as industrial energy, sun power has the low shortcoming of energy density, and in order to make full use of this cheapness, environmental protection, reproducible new forms of energy, produce solar photocell cheap, efficient, the ability large-area preparation is the target that people pursued always.
At present, silica-based and other inorganic metal compound solar photocells main flow that is solar cells.Although yet production cost declines to a great extent in recent years, the cost problem remains its major obstacle that significantly replaces traditional energy.Because the inorganic solar cell production process is complicated, the very difficulty that further significantly reduces cost, the problems such as the limit of cost height and effciency of energy transfer are restricted its large-scale promotion.
Utilizing the solar cell of photovoltaic effect carrying out to raise the efficiency and to reduce cost as the energy transformation device is the research of target, and the fast development of conjugation conducting polymer composite makes research and development low-cost solar battery become possibility.Polymer solar battery has become one of this hot research fields because its cost is low, in light weight, preparation is convenient and have molecule sanction property.
Early stage polymer thin-film solar cell material mainly concentrates on the organic dye such as phthalocyanine 、 perylene, and battery structure is main with individual layer Schottky-barrier formula.The photoelectric transformation efficiency of Schottky-barrier battery is not high always, and reason is that the metal electrode major part that incident light is positioned at battery sandwich has reflected away.1986, Tang (C. W. Tang, Appl. Phys. Lett.; 1986; 48 (2): 183) employing has double-deck polymer thin-film solar cell (ITO/CuPc/PV/Ag) first, and photoelectric transformation efficiency reaches 1% first, and packing factor also reaches 0.65.In this bilayer structure polymer thin-film solar cell, the photovoltaic performance of battery is by the interface of two kinds of polymkeric substance but not the interface of electrode/polymer materials decision.Compare the Schottky-barrier battery; Polymkeric substance p-n heterojunction bilayer structure battery has many advantages; Can prepare the device of wide spectral response range to the choose reasonable of polymer materials, various polymeric donors, acceptor material make the high yield of photoproduction charged carriers become possibility.1992, and Sariciftci etc. (Sariciftci N S, Heeger A J, Science, 1992,258:1474) find conjugated polymers and C
60Between photoinduction transfer transport phenomenon, when the energy of incident light during, conjugated polymers deposits yields photoproduction exciton greater than π-π *, from excited state to the charge transfer to C
60On occur as Pi Miaoji.C
60The pl-that makes conjugated polymers is by cancellation, and this makes C
60Be applied to optical sensor and solar cell becomes possibility.Since then, the conjugated polymers electrooptical device has obtained the attention of academia.Yu Gang (Yu G, Heeger A J, Appl Phys Lett, 1994,64 (25): 3422-3423) with C
60Mix with MEH-PPV, process MEH-PPV/C
60Blend film structure solar cell, effciency of energy transfer significantly improves than bi-layer devices.Because electron donor(ED) and electron acceptor(EA) be the network-like external phase of each self-forming mutually; The electronics that photoinduction produced and hole can be respectively separately mutually in carry and form network-like external phase; The electronics that photoinduction produced and hole can be respectively separately mutually in carry and on corresponding electrode, be collected; Photo-generated carrier is greatly reduced by compound probability again before arriving corresponding electrode, so photo-quantum efficiency reaches 1000 to 10000 times of pure MEH-PPV.Yet because C
60Limited solubility and easy crystallinity, MEH-PPV/C
60The performance of blend film is difficult for optimizing.With the higher C of solubility
60Verivate PCBM replaces the C in the blending structure
60, photovoltaic energy conversion efficient can obviously improve.To the MEH-PPV/PCBM system, can obtain 3% effciency of energy transfer.1998, (M. Granstrom, K. Petritsch such as Granstrom; A. C. Arias; At al., Nature, 1998; 395:257) with regular n-octyl phenyl substituting polythiophene verivate (POPT) as electron donor material, replace polyphenylvinylenes (MEH-CN-PPV) replaced C with blue cyanic acid
60Prepared sensitive cell as electron acceptor(EA).Find blend single layer device external quantum efficiency only 0.05%, only be equivalent to MEH-CN-PPV single layer device efficient.Estimation is because thermal treatment or the solvent treatment of POPT make individual layer blend MEH-CN-PPV/POPT device be separated the situation variation.Calendar year 2001, Saricifitci study group (S. E. Shaheen, C. J. Brabec; N. S. Saricifitci; Et. al., Appl. Phys. Lett. 2001 is 78:841) at effciency of energy transfer and conjugated polymers and C based on polymer thin-film solar cell
60There is the understanding of substantial connection in the pattern of verivate (mainly referring to PCBM) blend, has prepared conjugated polymers and C
60The verivate microfacies is mixed extraordinary device, has obtained 2.5% effciency of energy transfer (AM1.5).It is fine that the reason that produces this good result is that device two mixes mutually.2002, the effciency of energy transfer of this solar cell reached 3% especially (C. J. Brabec, S. E. Shaheen, C. Winder, N. S. Sariciftci, et. al., Appl. Phys. Lett. 2002,80:1288).
Conjugated polymers as electron donor(ED) and hole transport body; Polyvinyl carbazole (PVK) is arranged, gather vinylbenzene (PPV), polyaniline (PANI), polypyrrole (PPy), polyacetylene (PA), Polythiophene (PTh) etc.; Wherein polythiophene class (PTh) is one type of comparatively popular material of Recent study, and wherein better performances is to gather 3-alkylthrophene (P
3AT), generally contain the above alkylthrophene solubilized of 6 carbon atoms, but the alkyl substituent below 10 carbon there is part to be gel.The stronger sulphur atom of electron-withdrawing power is arranged on the polythiophene class main chain, and maximum absorption band is near 600nm, with the solar spectrum comparison match.In addition, the polythiophene class verivate also has higher hole mobility, and this is very helpful for improving effciency of energy transfer.
Certainly, improve the effciency of energy transfer of whole solar cell, the optimised devices structure also is vital.Four kinds of device architectures based on the conjugated polymer photovoltaic cell: (a) individual layer photovoltaic cell (photoactive layer only is made up of conjugated polymer, and often appearance is compound in carrier transport process, and efficient is lower); (b) double-deck photovoltaic cell (photoactive layer is made up of conjugated polymer and corresponding electron acceptor(EA), and is low to the utilising efficiency of conjugated polymer); (c) unordered bulk heterojunction (photoactive layer is formed by conjugated polymer and the unordered blend of electron acceptor(EA), and exciton dissociation efficient is high, but is prone to form isolated island, and transmission range is also longer, and power loss is bigger); (d) (photoactive layer is formed by conjugated polymer and the self-assembly of electron acceptor(EA) ordered nano orderly bulk heterojunction; Heterojunction extensively is present in two-phase interface; Exciton dissociation efficient is high, and carrier transport is the device architecture of present ideal polymer solar battery film of generally acknowledging apart from weak point).Wherein, Individual layer and bilayer structure are because its born defective is eliminated, and then both belong to the bulk heterojunction photo-conductive film, have very big exciton separating interface; Make most excitons can access effective separation, both make polymer solar battery after now the employing more.So-called bulk heterojunction photo-conductive film is accepted material (being generally the high inorganic semiconductor material of electric transmission rate) blend with electron donor material (being generally conjugated polymer) and electronics exactly; Formation has the photo-conductive film material of two phase continuous structures, and promptly the biphase phase interface is all heterojunction.Can know that through theoretical calculating the device architecture that most possibly reaches the commercialization utilization is exactly orderly bulk heterojunction, is expected to reach 10% effciency of energy transfer.
Up to the present, form orderly bulk heterojunction and mainly contain following several method: the one, blending method is through with electron donor(ED) such as Polythiophene etc. and electron acceptor(EA) such as C
60After carrying out blend, and carry out aftertreatment and obtain orderly bulk heterojunction, the shortcoming of this method is the difficult control of post-treatment condition, and in use the stability of film is also relatively poor; The 2nd, through the microemulsion blending method, though this method can be controlled the yardstick of microfacies comparatively easily, be difficult to remove the tensio-active agent that remains on the microfacies interface, thereby the separate electronic hole is right effectively; The 3rd, hard template method, through spin coating organic electronic donor (like P3HT) in the nanoporous template (like the titanium oxide template) of inorganic electronic acceptor, thereby this method causes the polymer segment torsional deformation to reduce the photovoltaic efficiency of conversion easily; The 4th, through the microphase-separated method of segmented copolymer; This method not only can effectively be controlled the yardstick of microfacies through adjusting each segmental length; And the film that forms has satisfactory stability property; Yet present this method did not also have report at the segmented copolymer that the application of organic photovoltaic also seldom has report, especially main chain to comprise soccerballene.
Summary of the invention
The objective of the invention is to overcome the deficiency that prior art exists, the preparation method and the film thereof of the segmented copolymer that a kind of main chain contains soccerballene is provided.
The main chain that the present invention proposes contains the segmented copolymer of soccerballene; It by soccerballene, gather the basic thiophene of alkane (oxygen) and POLYACTIC ACID is formed; This segmented copolymer can be in film process under controlled yardstick spontaneous formation micro phase separation structure; Electron-hole pair is separated on the microfacies interface effectively; And soccerballene is arranged in as electron acceptor material on the interface of microfacies in an orderly manner, has greatly saved the usage quantity of expensive soccerballene, and the micro phase separation structure that forms through this method possesses satisfactory stability property.
A kind of main chain that the present invention proposes contains the preparation method of the segmented copolymer of soccerballene, and this method at first utilizes the GRIM method to prepare the regular end to end basic thiophene of alkane (oxygen) that gathers, and obtains C through the Vilsmeier-Haack reaction then
60End cappedly gather the basic thiophene of alkane (oxygen), and then connect the 4-hydroxy benzaldehyde, and it is caused the rac-Lactide ring-opening polymerization as macromole evocating agent in the presence of catalyzer, finally obtain the segmented copolymer that a kind of main chain comprises soccerballene.Concrete steps are following:
(1) in the 250ml there-necked flask, add 50～150ml anhydrous organic solvent, 5～25mmol 2, and 5-two bromo-alkylated substituted thiazoline fens or alkoxyl group substituted thiophene and 5～25mL concentration are the tetrahydrofuran solution of 1M methyl-magnesium-bromide, 75 ℃ of refluxed 1～3h.Add 0.09～0.36mmol diphenylphosphine propane nickelous chloride (Ni (dppp) Cl
2), stir 0.5～6h.Slowly add 50～150mg lithium aluminum hydride (LiAlH
4) termination reaction.Excessive LiAlH
4Remove through dropwise dripping the hydrochloric acid that concentration is 1M (HCl).Reaction solution is poured methanol extraction into; 3000～8000rpm spinning, and use methyl alcohol (to remove monomer and salt), hexane (to remove catalyzer and oligopolymer) and chloroform to carry out Suo Shi respectively and extract is poured methyl alcohol into after at last the chloroformic solution of product being concentrated and is precipitated once more; 3000～8000rpm spinning; 30 ~ 60 ℃ of following drying under reduced pressure obtain gathering the basic substituted thiophene of alkane (oxygen) (PAT), and productive rate is 50%～85%.
(2) get 200～400mg and gather the basic thiophene of alkane (oxygen) (PAT) in two mouthfuls of reaction flasks of 100mL, add 10～20mL anhydrous organic solvent, vacuumize logical nitrogen three deoxygenations repeatedly, slowly be heated to 50 ~ 90 ℃ under the magnetic agitation and dissolve fully until PAT.Add 1500～3000 μ L N-methyl formyl anilines and 250～500 μ L Phosphorus Oxychlorides with disposable syringe.After stirring 24～72h under 50 ~ 90 ℃ of nitrogen protections, be chilled to room temperature (25 ℃), stir the saturated sodium acetate solution of 10～20mL that adding down prepares in advance, continue to stir 2～6h.Reaction solution is poured in the separating funnel, upper oil phase is divided into 100～200mL absolute ethyl alcohol deposition, 3000 ~ 8000rpm spinning goes out product, and 30 ~ 60 ℃ of following vacuum-dryings obtain the end capped PAT of aldehyde radical (diCHO-PAT), productive rate 85%～95%.
(3) get 100～200mg diCHO-PAT in two mouthfuls of flasks of 25mL, add 50～100mg sarkosine and 25～50mg soccerballene (C
60) and 5～15mL organic solvent, vacuumize logical three deoxygenations of nitrogen repeatedly, 30 ~ 60 ℃ are stirred until the diCHO-PAT dissolving fully down, are warming up to 80 ~ 120 ℃ of reaction 24～72h.Be chilled to after the room temperature with 25～75mL methanol extraction, 3000 ~ 8000rpm spinning throw out extracts throw out with normal hexane Suo Shi and removes excessive C
60, reduced pressure at room temperature obtains the end capped basic thiophene (diC of alkane (oxygen) that gathers of soccerballene
60-PAT), productive rate 85%～95%.
(4) get 50～100mg diC
60-PAT is in two mouthfuls of flasks of 25mL; Add 10～20mg PARA HYDROXY BENZALDEHYDE and 30～60mg sarkosine and 5～10mL organic solvent, be heated to 80 ~ 120 ℃, magnetic agitation 24～72h under stirring; With 25～50ml methanol extraction; 3000 ~ 8000rpm spinning, reduced pressure at room temperature obtains the end capped basic thiophene di of alkane (the oxygen) (C that gathers of hydroxyl soccerballene
60-OH)-and PAT, productive rate 85%～95%.
(5) get 50～100mg di (C
60-OH)-and PAT, 100～200mg D, L-rac-Lactide, 5～10mg stannous octoate (Sn (oct)
2) in two mouthfuls of flasks of 25mL; Add 5～15mL organic solvent; Slowly be warming up to 60 ~ 100 ℃ under the magnetic agitation, pour reaction solution into methanol extraction behind reaction 36～72h, 3000 ~ 8000rpm spinning goes out throw out; Reduced pressure at room temperature 6 ~ 48h obtains gathering the basic thiophene-soccerballene of alkane (oxygen)-polylactic acid triblock copolymer (di (PLA-C
60)-PAT), productive rate 50%～60%.
Among the present invention, it can be one to multiple kind in chloroform, methylene dichloride, toluene, YLENE, benzene, hexanaphthene, octane-iso, trimethylpentane, pentamethylene, Butyryl Chloride, trieline, propyl ether, ETHYLE ACETATE, butylacetate, Ethylene Dichloride, dioxane or the THF that organic solvent described in step (1), (2), (4) and (5) is respectively described organic solvent.
Among the present invention; Said alkylated substituted thiazoline fen; Can be the fen of 3-alkylated substituted thiazoline or 3,4-dialkyl group substituted thiophene, for example 3-butyl substituted thiophene, 3-isopentyl substituted thiophene, 3-n-pentyl substituted thiophene, 3-hexyl substituted thiophene, 3-octyl group substituted thiophene, 3-iso-octyl substituted thiophene, 3-(2-ethyl) hexyl substituted thiophene, 3-dodecyl substituted thiophene, 3; 4-two (isopentyl) substituted thiophene, 3,4-two (dodecyl) substituted thiophene etc.; Said alkoxyl group substituted thiophene; Can be the replacement of 3-alkoxyl group or 3; 4-dialkoxy substituted thiophene, for example 3-methoxyl group substituted thiophene, 3-pentyloxy substituted thiophene, 3-octyloxy substituted thiophene, 3-(dodecyl) thiophene-3-(pentyloxy) thiophene copolymers, 3-(dodecyl) thiophene-3-(octyloxy) thiophene copolymers etc.
The present invention contains the film of the segmented copolymer of soccerballene for a kind of main chain.The segmented copolymer that this method contains a kind of main chain soccerballene is mixed with particular concentration with specific solvent; Form the film of different thickness in certain stromal surface through the method for spin coating; And form orderly nano-porous structure through certain post-processing, can be used for the organic photovoltaic field of materials.
A kind of main chain that the present invention proposes contains the film of the segmented copolymer of soccerballene, and concrete steps are following:
(1) gets 10 ~ 50mg di (PLA-C
60)-PAT is dissolved in 0.5 ~ 5mL 1, the 2-dichlorobenzene, and stirred overnight under the nitrogen protection, subsequent use.
(2) used acetone, chloroform and Virahol ultrasonic cleaning conductive matrices successively 5 ~ 30 minutes, nitrogen drying.With above-mentioned di (PLA-C
60)-PAT solution is added drop-wise to the conductive matrices surface through 0.25 ~ 0.85 micron filter tip; Treat after the complete drawout of drop; Open in rotary coating machine 2～10s and be increased to 500～2000rpm from 0; Keep 500～2000rpm, 20～60s, wet film is transferred to petri dish evaporate slowly, be controlled at 0.5～2h time of drying thereby make.After treating the film drying, it is transferred to 120 ~ 180 ℃ of annealing 1～5h in the nitrogen atmosphere, the film thickness after the annealing is 20～100nm.
(3) compound concentration is water/methanol solution of the NaOH of 0.5 ~ 5M, and wherein water/methyl alcohol volume ratio is 1/4～4/1, and is subsequent use.
(4) under the room temperature respectively with the water of above-mentioned NaOH/methanol solution degraded PLA segment 12～72 hours, clean up with deionized water, compressed nitrogen is fully dry.
Among the present invention, said conductive matrices be conduction tinsel, ito glass or above scribble the polyester chips of conducting medium or drum type, zonal conducting metal or electrical conductivity alloy.
Advantage of the present invention is: 1. the present invention contains the segmented copolymer of soccerballene for a kind of main chain; It by soccerballene, gather alkane (oxygen) thiophene and POLYACTIC ACID is formed; This segmented copolymer can be in film process under controlled yardstick spontaneous formation micro phase separation structure; Electron-hole pair is separated on the microfacies interface effectively, and the micro phase separation structure that forms through this method possesses satisfactory stability property; 2. soccerballene is arranged in as electron acceptor material on the interface of microfacies in an orderly manner, has greatly saved the usage quantity of expensive soccerballene; Advantage such as preparation method 3. of the present invention has that technology is easy, quality of forming film is high, input-output ratio is high, with low cost and application prospect is extensive; The product that utilizes the present invention to prepare; Be new generation of green environment-friendly and high-performance Chemicals, can be used for the organic photovoltaic field of materials.
Description of drawings
Fig. 1 gathers 1 of (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer, 2-dichlorobenzene solution photo, and Zuo Weiju (3-hexyl thiophene), right for gathering (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer.
Fig. 2 is the photo in kind that gathers (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer film, (a) for gathering (3-hexyl thiophene) film photo, (b) for gathering (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer film photo.
Fig. 3 is the AFM 3D rendering that gathers (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer film, (a) for before the polylactic acid chain segment degraded, (b) for after the polylactic acid chain segment degraded.
Fig. 4 is the fluorescence emission spectrogram that gathers (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer film.
Embodiment
Embodiment 1
The preparation main chain contains the segmented copolymer of soccerballene, and concrete steps are following:
(1) in the 250ml there-necked flask, add the 150ml anhydrous tetrahydro furan, 16mmol 2, and 5-two bromo-3-hexyl thiophenes and 16mL concentration are the tetrahydrofuran solution of the methyl-magnesium-bromide of 1M, 75 ℃ of refluxed 3h.Add 0.36mmol diphenylphosphine propane nickelous chloride (Ni (dppp) Cl
2), stir 6h.Slowly add 150mg lithium aluminum hydride (LiAlH
4) termination reaction, excessive LiAlH
4Through dropwise dripping concentration is that 1M hydrochloric acid (HCl) is removed.Reaction solution is poured methanol extraction into; 4000rpm spinning, and use methyl alcohol (to remove monomer and salt), hexane (to remove catalyzer and oligopolymer) and chloroform to carry out Suo Shi respectively and extract is poured methyl alcohol into after at last the chloroformic solution of product being concentrated and is precipitated once more; The 4000rpm spinning; 50 ℃ of following drying under reduced pressure are gathered (3-hexyl thiophene) (P3HT), and productive rate is 85%.
(2) get 400mgP3HT in two mouthfuls of reaction flasks of 100mL, add the 20mL dry toluene, vacuumize logical nitrogen three deoxygenations repeatedly, slowly be heated to 75 ℃ under the magnetic agitation and dissolve fully until P3HT.Add 3000 μ L N-methyl formyl anilines and 500 μ L Phosphorus Oxychlorides with disposable syringe.After stirring 72h under 75 ℃ of nitrogen protections, be chilled to room temperature (25 ℃), stir the saturated sodium acetate solution of 20mL that adding down prepares in advance, continue to stir 6h.Reaction solution is poured in the separating funnel, upper oil phase is divided into 200mL absolute ethyl alcohol deposition, the 4000rpm spinning goes out product, and 50 ℃ of following vacuum-dryings obtain the end capped P3HT of aldehyde radical (diCHO-P3HT), productive rate 95%.
(3) get 200mg diCHO-P3HT in two mouthfuls of flasks of 25mL, add 100mg sarkosine and 50mg soccerballene (C
60) and 15mL toluene, vacuumize logical three deoxygenations of nitrogen repeatedly, 50 ℃ are stirred until the diCHO-P3HT dissolving fully down, are warming up to 100 ℃ of reaction 72h.Use the 75mL methanol extraction after being chilled to room temperature, 4000rpm spinning throw out extracts throw out with normal hexane Suo Shi and removes excessive C
60, reduced pressure at room temperature obtains the end capped P3HT (diC of soccerballene
60-P3HT), productive rate 95%.
(4) get 100mg diC
60-P3HT adds 20mg PARA HYDROXY BENZALDEHYDE and 60mg sarkosine and 10mL toluene in two mouthfuls of flasks of 25mL, be heated to 100 ℃ under stirring; Magnetic agitation 72h uses the 50ml methanol extraction, the 4000rpm spinning; Reduced pressure at room temperature obtains the end capped P3HT of hydroxyl soccerballene (di (C
60-OH)-P3HT), productive rate 95%.
(5) get 100mg di (C
60-OH)-and P3HT, 200mg D, L-rac-Lactide, 10mg stannous octoate (Sn (oct)
2) in two mouthfuls of flasks of 25mL; Add 15mL toluene; Slowly be warming up to 80 ℃ under the magnetic agitation, pour reaction solution into methanol extraction behind the reaction 72h, the 4000rpm spinning goes out throw out; Reduced pressure at room temperature 24h is gathered (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer (di (PLA-C
60)-P3HT), productive rate 60%.
The segmented copolymer that the main chain that above-mentioned preparation method is obtained contains soccerballene carries out film forming, and concrete steps are following:
(1) gets 25mg di (PLA-C
60)-P3HT is dissolved in 1mL 1, the 2-dichlorobenzene, and stirred overnight under the nitrogen protection, subsequent use.
Used acetone, chloroform and Virahol ultrasonic cleaning ito glass successively 10 minutes, nitrogen drying.With above-mentioned di (PLA-C
60)-P3HT solution is added drop-wise to the ito glass surface through 0.45 micron filter tip; Treat after the complete drawout of drop; Open in the rotary coating machine 10s and be increased to 2000 rpm from 0; Keep 2000 rpm 60s, wet film is transferred to petri dish evaporate slowly, thereby be controlled at about 2h time of drying.After treating the film drying, it is transferred to 165 ℃ of annealing 5h in the inert atmosphere, the film thickness after the annealing is 20nm.
(2) compound concentration is water/methanol solution of the NaOH of 1M, and wherein water/methyl alcohol volume ratio is 1/4.Subsequent use.
(3) under the room temperature respectively with the water of above-mentioned NaOH/methanol solution degraded PLA segment 72 hours, use washed with de-ionized water, the compressed nitrogen drying.
This photo in kind that gathers (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer solution is as shown in Figure 1; Fig. 2 and Fig. 3 are respectively its photo in kind and AFM 3D rendering, and this fluorescence emission spectrogram that gathers (3-hexyl thiophene)-soccerballene-polylactic acid triblock copolymer film is Fig. 4.
Embodiment 2
Identical with embodiment 1, but the rac-Lactide consumption becomes 100mg.The photosensitive property of this triblock copolymer film is seen Fig. 4.
Embodiment 3
Identical with embodiment 1, but the rac-Lactide consumption becomes 150mg.
Embodiment 4
Identical with embodiment 1, but the 3-hexyl thiophene becomes 3-octyl group substituted thiophene.
Embodiment 5
Identical with embodiment 1, but the 3-hexyl thiophene becomes 3,4-two (isopentyl) substituted thiophene.
Embodiment 6
Identical with embodiment 1, but the diphenylphosphine propane nickelous chloride becomes 0.09mmol.
Embodiment 7
Identical with embodiment 1, but the diphenylphosphine propane nickelous chloride becomes 0.18mmol.
Embodiment 8
Identical with embodiment 1, but conductive matrices changes metallic aluminium into by the ito glass sheet.
Embodiment 9
Identical with embodiment 1, but organic solvent becomes THF by chloroform.
Embodiment 10
Identical with embodiment 1, but organic solvent becomes toluene by chloroform, and annealing time becomes 1 hour.
Embodiment 11
Identical with embodiment 1, but the triblock copolymer film thickness becomes 100nm by 20nm.
Embodiment 12
Identical with embodiment 1, but the triblock copolymer film thickness becomes 50nm by 20nm.
The main chain that obtains among the embodiment 2-12 comprises the segmented copolymer film of soccerballene and the film of embodiment 1 has similar performance.
Claims (5)
1. a main chain contains the preparation method of the segmented copolymer film of soccerballene, it is characterized in that concrete steps are:
(1) in the 250ml there-necked flask, adds 50～150ml anhydrous organic solvent; 5～25mmol 2; 5-two bromo-alkylated substituted thiazoline fens or 2,5-two bromo-alkoxyl group substituted thiophenes and 5～25mL concentration are the tetrahydrofuran solution of 1M methyl-magnesium-bromide, 75 ℃ of refluxed 1～3h; Add 0.09～0.36mmol diphenylphosphine propane nickelous chloride, stir 0.5～6h; Slowly add 50～150mg lithium aluminum hydride termination reaction; Excessive LiAlH
4Through dropwise dripping concentration is that the hydrochloric acid of 1M is removed; Reaction solution is poured methanol extraction into; 3000～8000rpm spinning; And carry out Suo Shi with methyl alcohol, hexane and chloroform respectively and extract, pour methyl alcohol into after at last the chloroformic solution of product being concentrated and precipitate 3000～8000rpm spinning once more; 30-60 ℃ of following drying under reduced pressure obtains gathering the alkylated substituted thiazoline fen or gathers the alkoxyl group substituted thiophene;
(2) getting 200～400mg gathers the alkylated substituted thiazoline fen or gathers the alkoxyl group substituted thiophene in two mouthfuls of reaction flasks of 100mL; Add 10～20mL anhydrous organic solvent; Vacuumize logical nitrogen three deoxygenations repeatedly, slowly be heated to 50-90 ℃ under the magnetic agitation and dissolve fully until gathering the alkylated substituted thiazoline fen or gathering the alkoxyl group substituted thiophene; Add 1500～3000 μ L N-methyl formyl anilines and 250～500 μ L Phosphorus Oxychlorides with disposable syringe; After stirring 24～72h under the 50-90 ℃ of nitrogen protection, be chilled to 25 ℃, stir the saturated sodium acetate solution of 10～20mL that adding down prepares in advance, continue to stir 2～6h; Reaction solution is poured in the separating funnel, upper oil phase is divided into 100～200mL absolute ethyl alcohol deposition, the 3000-8000rpm spinning goes out product, and 30-60 ℃ of following vacuum-drying obtains that aldehyde radical is end capped to be gathered the alkylated substituted thiazoline fen or gather the alkoxyl group substituted thiophene;
(3) get that 100～200mg aldehyde radical is end capped to be gathered the alkylated substituted thiazoline fen or gather the alkoxyl group substituted thiophene in two mouthfuls of flasks of 25mL; Add 50～100mg sarkosine and 25～50mg soccerballene and 5～15mL organic solvent; Vacuumize logical three deoxygenations of nitrogen repeatedly; 30-60 ℃ is stirred down until aldehyde radical is end capped and gathers the alkylated substituted thiazoline fen or gather the dissolving of alkoxyl group substituted thiophene fully, is warming up to 80-120 ℃ of reaction 24～72h; Be chilled to after the room temperature with 25～75mL methanol extraction; 3000-8000rpm spinning throw out extracts throw out with normal hexane Suo Shi and removes excessive soccerballene, reduced pressure at room temperature; Obtain that soccerballene is end capped to be gathered the alkylated substituted thiazoline fen or gather the alkoxyl group substituted thiophene, productive rate 85%～95%;
(4) get that 50～100mg soccerballene is end capped to be gathered the alkylated substituted thiazoline fen or gather the alkoxyl group substituted thiophene in two mouthfuls of flasks of 25mL, add 10～20mg PARA HYDROXY BENZALDEHYDE and 30～60mg sarkosine and 5～10mL organic solvent, be heated to 80-120 ℃ under stirring; Magnetic agitation 24～72h; With 25～50ml methanol extraction, 3000-8000rpm spinning, reduced pressure at room temperature; Obtain that hydroxyl soccerballene is end capped to be gathered the alkylated substituted thiazoline fen or gather the alkoxyl group substituted thiophene, productive rate 85%～95%;
(5) get that the hydroxyl soccerballene of 50～100mg is end capped to be gathered the alkylated substituted thiazoline fen or gather alkoxyl group substituted thiophene, 100～200mg D; L-rac-Lactide, 5～10mg stannous octoate are in two mouthfuls of flasks of 25mL; Add 5～15mL organic solvent, slowly be warming up to 60-100 ℃ under the magnetic agitation, pour reaction solution into methanol extraction behind reaction 36～72h; The 3000-8000rpm spinning goes out throw out; Reduced pressure at room temperature 6-48h obtains gathering alkylthrophene-soccerballene-polylactic acid triblock copolymer or gathers alkoxy thiophene-soccerballene-polylactic acid triblock copolymer, productive rate 50%～60%.
2. preparation method according to claim 1 is characterized in that saidly 2, and 5-two bromo-alkylated substituted thiazoline fens are 2; 5-two bromo-3-alkylated substituted thiazoline fens or 2,5-two bromo-3,4-dialkyl group substituted thiophene; Said 2,5-two bromo-alkoxyl group substituted thiophenes are 2,5-two bromo-3-alkoxyl group substituted thiophenes or 2; 5-two bromo-3,4-dialkoxy substituted thiophene.
3. preparation method according to claim 1 is characterized in that said organic solvent is an one to multiple kind in chloroform, methylene dichloride, toluene, YLENE, benzene, hexanaphthene, octane-iso, trimethylpentane, pentamethylene, Butyryl Chloride, trieline, propyl ether, ETHYLE ACETATE, butylacetate, Ethylene Dichloride, dioxane or the THF.
One kind according to claim 1 the main chain that obtains of preparation method contain the film that the segmented copolymer of soccerballene carries out, it is characterized in that concrete steps are following:
(1) get the segmented copolymer that the said main chain of 10-50mg contains soccerballene and be dissolved in 0.5-5mL 1, the 2-dichlorobenzene, stirred overnight under the nitrogen protection, subsequent use;
(2) used acetone, chloroform and Virahol ultrasonic cleaning conductive matrices successively 5-30 minute, nitrogen drying; The block copolymer solution that above-mentioned main chain is contained soccerballene is added drop-wise to the conductive matrices surface through 0.25-0.85 micron filter tip; Treat after the complete drawout of drop; Open in rotary coating machine 2～10s and be increased to 500～2000rpm from 0; Keep 500～2000rpm, 20～60s, wet film is transferred to petri dish evaporate slowly, be controlled at 0.5～2h time of drying thereby make; After treating the film drying, it is transferred to 120-180 ℃ of annealing 1～5h in the nitrogen atmosphere, the film thickness after the annealing is 20～100nm;
(3) compound concentration is water/methanol solution of the NaOH of 0.5-5M, and wherein water/methyl alcohol volume ratio is 1/4～4/1, and is subsequent use;
(4) under the room temperature respectively with the water of above-mentioned NaOH/methanol solution degraded PLA segment 12～72 hours, clean up with deionized water, compressed nitrogen is fully dry.
5. film according to claim 4, it is characterized in that said conductive matrices be conduction tinsel, ito glass or above scribble the polyester chips of conducting medium, or in drum type, zonal conducting metal or the electrical conductivity alloy any.
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