CN102504273B - Poly 3-hexylthiophene triblock copolymer with rod-line-rod structure - Google Patents
Poly 3-hexylthiophene triblock copolymer with rod-line-rod structure Download PDFInfo
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- CN102504273B CN102504273B CN201110337817.4A CN201110337817A CN102504273B CN 102504273 B CN102504273 B CN 102504273B CN 201110337817 A CN201110337817 A CN 201110337817A CN 102504273 B CN102504273 B CN 102504273B
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Abstract
The invention relates to poly 3-hexylthiophene triblock copolymer with a rod-line-rod structure, which is characterized by having the following chemical structural formula, wherein in the formula, n is in the range of 30 to 100, m is in the range of 10 to 150 and R is selected from H+, -CH2CH2CH2CH3, -CH3 or -CH2CH(CH3)2. The polymer has both the photoelectric characteristic of P3HT (polythiophene) and the flexibility of a middle linear segment. Meanwhile, the influence of the line end in a line-rod structure on the photoelectric property of the P3HT is eliminated. The P3HT copolymer with the rod-line-rod structure is mainly applied to the fields of a light emitting diode, a solar cell, a photoelectric sensor and the like.
Description
One, technical field
The present invention relates to a kind of three block photoelectric semiconductor materials, the definite P3HT class triblock copolymer that says a kind of rod-line-bar structure.
Two, background technology
Polythiophene and derivative thereof have caused people's extensive concern in the application in the fields such as solar cell, photodiode, photo-sensor, electromagnetic shielding in recent years.In Polythiophene extended familys, poly-3-hexyl thiophene (P3HT) has good solubility, processibility, environmental stability with it, and compound with regular structure is easy to get, synthesis step is the excellent over-all properties and be considered to one of best photoconductive organic semiconductor material such as simply.
The crystal habit of polymkeric substance directly affects the electrical properties of material, and therefore the new method of exploitation control polymer morphology has huge development potentiality.For further promoting the performance of P3HT, the P3HT for preparing block structure has been proved to be as one of effective method.The P3HT of two block line-bar structures and three block line-rod-line structures is produced out.Its preparation method is mainly divided into take the P3HT of end-functionalization and is the situ aggregation method (being grafting-from method) of the combination living polymerization that reaction is basic, and the linear polymer of functionalization P3HT and functionalization is by the chemical reaction synthesis method (being grafting-to method) of end group.The former is owing to there being severe reaction conditions, and polymerizable molecular structural controllability is poor and be difficult to be applied among actual application.
It in the grafting-to method of the preparation of P3HT block polymerization, is the new polymerization thinking of the P3HT segmented copolymer that proposed by Eric Cloutet etc.ATRP and 1, the general character that 3 Dipolar Cycloaddition have due to the advantage possessing separately and some aspect, by the method for two kinds of technology couplings, not only reaction conditions is gentle, products collection efficiency is high, and stereoselectivity is good, easily purifying, and molecular weight is controlled, therefore molecular weight distribution is narrower, and in CRP, ATRP becomes with click chemistry coupling and prepares the most widely used a kind of polymerization process of special construction polymer.Make them aspect the block polymerization of preparation P3HT line-bar structure, there is its unique application prospect, and approved widely.
Click chemistry (click chemistry) is a synthetic concept of being introduced in calendar year 2001 by chemist Sharpless, mainly refers to that the splicing by junior unit realizes the synthetic of fast and reliable various compounds.The representative reaction of click chemistry is 1 between Cu (I) compound for catalysis triazo-compound and alkynyl compounds, 3-Dipolar Cycloaddition, it can get up two kinds of different substancess by five-ring covalent attachment, the method possesses that productive rate is high, side reaction is few and nuisanceless, the advantage such as the gentle speed of response of reaction conditions is fast, is therefore widely used.The development of click chemistry is at present very rapid, has related to every field, particularly at aspects such as functional polymer, DNA, finishing, biological medicines, has obtained the achievement of attracting attention.
Synthetic report about P3HT segmented copolymer mainly contains: (the Macromolecules such as McCullough, 2007,40,4733) by reversible addition-fragmentation chain transfer free radical polymerization and Nitroxide free radical polymerisation process, synthesized line-excellent polymer P 3HT-b-PS and P3HT-b-PI, synthetic polymkeric substance forms nano thread structure by self-assembly; The people (Macromolecules, 2008,41,7033) such as Eric Cloutet are by atom transfer radical polymerization and 1, and 3-Dipolar Cycloaddition has been synthesized P3HT-PS and PS-P3HT-PS.People (the Polym.Chem. such as Christopher W.Bielawski, 2010,10,1039 and Chem.Commun., 2011,47,197 – 199) also by atom transfer radical polymerization and 1,3-Dipolar Cycloaddition has been synthesized a series of two block line-bar structure P3HT – block – PBLG, P3HT-b-PtBA and P3HT-b-PAA, self-assembly and solid-state structure to P3HT – block – PBLG in the aqueous solution are studied discovery, in solution its can be self-assembled into globosity solid crystals be filamentary structure.Someone reports out the P3HT of online-bar structure and line rod line structure, and it shows the special performance that is different from pure P3HT, with respect to the compound of the above two rod-line-bar structures but so far there are no any report
Three, summary of the invention
The present invention is directed to the defect of line-bar structure center line one end on poly-3-hexyl thiophene (P3HT) photoelectric properties impact, aim to provide a kind of rod-line-bar structure P3HT class triblock polymer, to overcome this defect.
The P3HT class triblock polymer of rod-line-bar structure that the present invention is alleged has following chemical structural formula:
N:30～100 in formula, m:10～150;
R is selected from H
+, methyl (CH
3), butyl (CH
2cH
2cH
2cH
3) or the tertiary butyl (CH
2cH (CH
3)
2).Preferably R is butyl; N:50～60, m:80～120.
The P3HT class triblock polymer of rod-line-bar structure that the present invention is alleged has following chemical structural formula:
N:30～100 in formula, m:10～150;
Preferred n:50～60, m:120～150.
The preparation method of this polymkeric substance (I) first prepares intermediate (1), be that one end is with P3HT(" rod " part of alkynyl), then prepare two azido polymers that intermediate (2) is compliant section (" line " part), last intermediate (1), (2) are by the synthetic target product (I) of 1,3-Dipolar Cycloaddition.
1, the preparation of intermediate (1) is with reference to McCullough method, and with the bromo-3-hexyl thiophene of 2,5-bis-, for monomer, THF is solvent, Ni (dppp) Cl
2for catalyzer carries out polymerization, after polymerization half an hour, add ethynyl bromination magnesium and be the synthetic one end of preparing of end-blocking with the effective P3HT(intermediate (1) of sense agglomerate base).Control polymerization degree n: 30～100.
Flow process is as follows:
2, the preparation of intermediate (2), take butyl acrylate as example, and flow process is as follows:
1. press document Chem.Commun., 2006,12, described in 5051, method is prepared nitrine propyl alcohol.Bromo propyl alcohol and sodiumazide are prepared nitrine propyl alcohol take reaction in the solution that DMF is solvent.
2. press document Macromolecules, 2008,41, the method described in 7033 is prepared the alpha-brominated isopropylformic acid nitrine of initiator propyl diester.With nitrine propyl alcohol and alpha-brominated isobutyl acylbromide, carry out esterification and prepare the alpha-brominated isopropylformic acid nitrine of initiator propyl diester.
3. take alpha-brominated isopropylformic acid nitrine propyl diester as initiator and butyl acrylate (nBA) by ATRP legal system for N
3-PnBA-Br.Control polymerization degree m:10～150.Polymerization degree m is determined by the initiator mol ratio different from monomer.
4. with N
3-PnBA-Br and reaction of sodium azide are prepared N
3-PnBA-N
3(intermediate (2)).
Experiment shows, the alpha-brominated isopropylformic acid nitrine of initiator propyl diester is except causing butyl acrylate, also can cause vinylformic acid, methyl acrylate, tert-butyl acrylate or cinnamic polymerization, and then generate the two-fold nitrogen polymer of compliant section (intermediate (2)) with reaction of sodium azide.
3, the synthetic target product (I) in intermediate (1) and (2):
4, after causing styrene polymerization, the alpha-brominated isopropylformic acid nitrine of initiator propyl diester generates the two-fold nitrogen polymer of compliant section (intermediate (2)) with reaction of sodium azide again, the synthetic target product (II) that obtains of last and intermediate (1).
Rod-line that the present invention prepares-bar structure P3HT class triblock polymer is with the photoelectric characteristic of P3HT and the flexibility of midium line segment, eliminated the impact of line-bar structure center line one end on P3HT photoelectric properties simultaneously, be mainly used in the fields such as organic photovoltaic cell, Organic Light Emitting Diode, photo-sensor, especially being suitable for preparing flexible organic semiconductor device, is the more satisfactory material that flexible TFT shows.
Four, accompanying drawing explanation
The compliant section N that Fig. 1 is Bifunctionalized
3-PnBA-N
3nuclear-magnetism figure.
The rod section P3HT-C of Fig. 2 monofunctional
2the nuclear-magnetism figure of H.
The nuclear-magnetism figure of Fig. 3 triblock copolymer P3HT-PnBA-P3HT.
Fig. 4 triblock copolymer P3HT-PnBA-P3HT is TFT device figure prepared by semiconductor material.
The transfer characteristic curve of Fig. 5 TFT device blend film.In figure, can see and distinguish obvious ON state and OFF state, the transistor regulating switch better performances making is described.
The output characteristic curve of Fig. 6 TFT device blend film.In figure, can see that obvious linear section and ， saturation region, saturation region can keep stable electric current, just because of this, transistor could keep steady state when trip switch, and this is one of required important requirement of transistor steady operation just.The volt-ampere characteristic that can regulate preferably drain electrode by regulation and control grid voltage, has realized transistorized function.
Note: the performance with Semiconductor Characterization System SCS-4200 test transistor, obtains source under different grid voltages, drain current voltage data is made Fig. 5 and Fig. 6.
Five, embodiment
(1). the preparation of compound (I)
Embodiment 1:R is the triblock copolymer of butyl acrylate
(1) preparation of intermediate (1):
The preparation of the P3HT of ethynyl list end-blocking is according to preparation method's preparation document (Macromolecules2005,38,10346) Suo Shu.With the bromo-3-hexyl thiophene of 2,5-bis-, for monomer, THF is solvent, Ni (dppp) Cl
2for catalyzer carries out polymerization, after polymerization half an hour, adding ethynyl bromination magnesium is that the synthetic one end of end-capping reagent is with the P3HT(intermediate (1) of piece base), control n:50～60.
(2) preparation of intermediate (2):
The preparation of nitrine propyl alcohol is according to method preparation document (Chem.Commun., 2006,12,5051) Suo Shu.
Initiator a-bromo acid nitrine propyl diester is according to the method preparation described in document (Macromolecules, 2008,41,7033).
The preparation of PnBA, take PMDETA/CuBr as catalyst system, and initiator: nBA is 1:100(mol ratio), adopt ATRP legal system for N
3-PnBA-Br.m：80～100。
Last N3-PnBA-Br reacts preparation N3-PnBA-N3 with NaN3.
(3) preparation of multipolymer
Intermediate (1), (2) are by the synthetic P3HT-PnBA-P3HT triblock copolymer (I) of 1,3-Dipolar Cycloaddition.Embodiment 2:R is acrylic acid triblock copolymer
In the middle of changing, compliant section polymer monomer is vinylformic acid, and according to the step of example 1, preparing R is acrylic acid triblock copolymer P3HT-PAA-P3HT.
Embodiment 3:R is the triblock copolymer of methyl acrylate
In the middle of changing, compliant section polymer monomer is methyl acrylate, according to the step of example 1, prepares the triblock copolymer P3HT-PMMA-P3HT that R is methyl acrylate.
Embodiment 4:R is the triblock copolymer of tert-butyl acrylate
In the middle of changing, compliant section polymer monomer is tert-butyl acrylate, according to the step of example 1, prepares the triblock copolymer P3HT-PtBA-P3HT that R is tert-butyl acrylate.
(2). the preparation of compound (II)
Embodiment 5:R is cinnamic triblock copolymer
In the middle of changing, compliant section polymer monomer is vinylbenzene, according to the step of example 1, prepares triblock copolymer P3HT-PS-P3HT.
(3). the homemade triblock copolymer of take is prepared TFT device and performance test thereof as organic semiconductor material
Get 8mg triblock copolymer P3HT-PnBA-P3HT and be dissolved in the THF of 4mL, washes clean a slice ito glass, spin on polymers solution on ito glass, in vacuum drying oven, 30 ℃ are dried one hour.Pass through afterwards mask plate vacuum evaporation gold electrode thereon, take out its performance of test.See Fig. 5, Fig. 6.
Claims (5)
1. a poly-3-hexyl thiophene class triblock copolymer for rod-line-bar structure, is characterized in that having following chemical structural formula:
N:30～100 in formula, m:10～150, R is selected from H
+,-CH
2cH
2cH
2cH
3,-CH
3or-CH
2cH (CH
3)
2.
2. multipolymer according to claim 1, is characterized in that: n:50～60, and m:100～120, R is-CH
2cH
2cH
2cH
3.
3. multipolymer according to claim 1 and 2, is characterized in that: n:50～60, m:80～120.
4. a poly-3-hexyl thiophene class triblock copolymer for rod-line-bar structure, is characterized in that having following chemical structural formula:
N:30～100 in formula, m:10～150.
5. multipolymer according to claim 4, is characterized in that: n:50～60, m:120～150.
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