CN109734879A - Two kinds contain isomers repetitive unit locally asymmetric conjugated polymer and preparation method thereof - Google Patents
Two kinds contain isomers repetitive unit locally asymmetric conjugated polymer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to two kinds to contain isomers repetitive unit locally asymmetric conjugated polymer and preparation method thereof.Main contents of the present invention first by containing unilateral bromine presoma respectively with TT-SnBu3, T-SnBu3Carry out Stille coupling polymerization, obtain two different molecules, then by after two molecules bilateral bromination of NBS with Me3Sn‑T‑SnMe3, Me3Sn‑TT‑SnMe3Polymerization obtains two kinds of asymmetric conjugated polymers in part containing isomers repetitive unit.Both polymer have preferable dissolubility, and uniform film is obtained after volatilization, there is relatively high mobility in the performance test of organic field effect tube.
Description
Technical field
The present invention relates to two kinds to contain isomers repetitive unit locally asymmetric conjugated polymer and preparation method thereof, belongs to
In organic field effect tube Material Field.
Background technique
The material category of organic field effect tube (Organic Field-Effect Transistor, OFET) is special
More, the type and quantity of especially symmetrical conjugatd polymers rapidly increase in recent years.But contain isomery weight
The asymmetric conjugated polymer in part of multiple unit is fewer and fewer at present.Full symmetric polymer solubility is very little, is not easy into
Film.On the contrary, perfectly asymmetric polymer solubility is too poor.The advantages of both polymer have concentrated them just show compared with
Good dissolubility, and stablize, the mobility of the organic field effect tube of test is also relatively high.
Summary of the invention
The purpose of the present invention is obtain dissolubility conjugated polymer appropriate by the skeleton construction for adjusting polymer.Institute
It is excellent that the asymmetric conjugated polymer in the part containing isomers repetitive unit stated has that mobility is high, chemical stability is good etc.
Point, this material have huge potential value in semiconductor field especially organic field effect tube direction.
To achieve the above object, the present invention adopts the following technical scheme:
Two kinds of asymmetric conjugated polymers in the part containing isomers repetitive unit, structural formula are as follows:
(1) and in (two) formula R is >=C20Saturation branched alkyl chain, Ar is pyridine, furans, five yuan or hexa-atomic miscellaneous of thiophene etc.
Ring, n > 0.
The present invention provides not only the asymmetric conjugated polymer in the part containing isomers repetitive unit, and also provides
The synthetic method of two polymer containing isomers repetitive unit.Mainly there are following steps:
(1) compound (such as 2- cyano thiophene, 2- cyanopyridine, 2- cyanofuran etc.) containing acetonitrile is molten with diethyl succinate
In tert-pentyl alcohol, under alkaline condition, 6 hours of heating reflux reaction generate the DPP compound A that bilateral has Ar base.
Wherein, Ar is furans, thiophene, five yuan of pyridine etc. or hexa-member heterocycle；
(2) bilateral has Ar base DPP compound A and halogenated alkane (>=C20Iodo be saturated branched-alkyl chain hydrocarbon) in organic solvent
In, under nitrogen atmosphere, 12 hours of heating reflux reaction.Deionized water quenching is added, crosses column purification, obtains containing alkyl chain
Compound B;
Wherein R is >=C20Saturation branched alkyl chain；Ar is furans, thiophene, five yuan of pyridine etc. or hexa-member heterocycle.
(3) in organic solvent by the obtained compound B containing alkyl chain of step (2), NBS is added at room temperature to carry out
Unilateral bromination, contact plate tracking reaction, obtains the presoma C containing unilateral bromine；
Wherein R is >=C20Saturation branched alkyl chain；Ar is furans, thiophene, five yuan of pyridine etc. or hexa-member heterocycle.
(4) by the obtained presoma C containing unilateral bromine of step (3) respectively with c group and d group substance dry organic
Anaerobic reaction is carried out in solvent, respectively obtains presoma D and E；
C group: Bu3Sn-T(2- tributylstamlyl thiophene), catalyst Pd2(dba)3, ligand P (o-Tolyl)3；
D group: Bu3Sn-TT(bibliography " Kawabata K, Takeguchi M, Goto H Optical
Activity of Heteroaromatic Conjugated Polymer Films Prepared by Asymmetric
Electrochemical Polymerization in Cholesteric Liquid Crystals: Structural
Function for Chiral Induction [J] Macromolecules, 2013,46 (6): 2078-2091. "), it urges
Agent Pd2(dba)3, ligand P (o-Tolyl)3；
Wherein R >=C20Saturation branched alkyl chain；Ar is furans, thiophene, pyridine or five-ring heterocycles.
(5) presoma D and E difference in step (4) at room temperature, are subjected to NBS bromination reaction in organic solvent,
Obtain monomer M1-1 and M1-2;
。
Wherein R >=C20Saturation branched alkyl chain；Ar is furans, thiophene, five yuan of pyridine etc. or hexa-member heterocycle.
(6) the monomer M1-1 and M1-2 in step (5) are assembled in the following manner,
A group: monomer M1-1, Me3Sn-TT-SnMe3(bis- (tributylestannyl) thieno [3,2-b] thiophene of 2,5-), are urged
Agent Pd2(dba)3, ligand P (o-Tolyl)3；
B group: monomer M1-2, Me3Sn-T-SnMe3(2,5-bis- (tin trimethyl) thiophene), catalyst Pd2(dba)3, ligand P
(o-Tolyl)3；
Two groups of substances of a and b are dissolved in dry toluene respectively, whole system under a nitrogen, is heated to reflux.After polymerization, by rope
Family name purifies, and it is respectively Polymer(mono- that vacuum drying, which obtains red solid polymer) and Polymer (two)
The structural formula of the asymmetric conjugated polymer in part containing isomers repetitive unit is as follows:
(1) R >=C and in (two) formula20Saturation branched alkyl chain, Ar is furans, thiophene, five yuan of pyridine etc. or hexa-member heterocycle, n
>0。
The synthesis of the above-described asymmetric conjugated polymer in the part containing isomers repetitive unit is in the anhydrous of routine
Carried out in toluene, the dissolubility of polymer is fine, in order to obtain preferably as a result, polymer in dependence test, use it is molten
Agent is chloroform reagent.
Innovative point and advantage of the invention
(1) the asymmetric conjugated polymer in part for obtaining the repetitive unit containing isomers, different from traditional asymmetry
Polymer.
(2) synthetic method of polymers is simple, and the yield of monomer and polymer is all very high.
(3) dissolubility of polymer is pretty good, is easily obtained high performance device film.
(4) polymer architecture seems simply, but different from the work of forefathers, it is a pair of polymerization that is simple and having no lack of innovation
Object.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of the presoma D in the embodiment of the present invention 4；
Fig. 2 is the nuclear magnetic resonance spectroscopy of the presoma E in the embodiment of the present invention 4；
Fig. 3 is the nuclear magnetic resonance spectroscopy of the monomer M1-1 in the embodiment of the present invention 5；
Fig. 4 is the carbon-13 nmr spectra of the monomer M1-1 in the embodiment of the present invention 5；
Fig. 5 is the nuclear magnetic resonance spectroscopy of the monomer M1-2 in the embodiment of the present invention 5；
Fig. 6 is the carbon-13 nmr spectra of the monomer M1-2 in the embodiment of the present invention 5；
Fig. 7 is Polymer (one) (PDPP-T) and Polymer (two) (PDPP-TT) infrared spectrum in the embodiment of the present invention 6；
Fig. 8 is Polymer (one) (PDPP-T) and Polymer (two) (PDPP-TT) uv atlas in the embodiment of the present invention 6, left
While being solution state, the right is filminess；
Fig. 9 is the structural schematic diagram of the organic thin film transistor device of organic semiconductor layer.
Specific embodiment
Synthetic method and product of the invention be not only a kind of, carries out specifically below in conjunction with practical operation step
It is bright.
1 bilateral of embodiment has the preparation of the DPP compound A of thiophene
7.72g potassium tert-butoxide is added in the 250ml there-necked flask for the tert-pentyl alcohol for filling 35ml, 105 DEG C of heating for dissolving, again property
4.3ml thiophene acetonitrile is injected, after reacting half an hour, 3.85ml diethyl succinate is added dropwise, the reaction was continued 6 hours, cold
But to 50 DEG C, 30ml methanol and 5ml acetic acid is added, is cooled to room temperature, is filtered with Bush's funnel, solid methanol and go from
Sub- water is washed, and is dried in vacuo a whole night, is obtained 3.2g brown solid substance.Since the substance dissolubility is too poor, Wu Fati
It is pure.Directly carry out next step reaction.
Specific implementation method bibliography " Lee, O. P.; Yiu, A. T.; Beaujuge, P. M.; Woo, C.
H.; Holcombe, T. W.; Millstone, J. E.; Douglas, J. D.; Chen, M. S.; Fréchet,
J. M. J. Adv. Mater. 2011,23 (45), 5359-5363.》
The preparation of compound B of the embodiment 2 containing side chain eicosane
3 g(10 mmol) bilateral has DPP compound A and 12.25 g (30 mmol) idoalkane (9- of thiophene
(iodomethyl) nonadecane) and 4.5 g (33 mmol) potassium carbonate be added in the two mouth flask of 250 ml,
120 ml DMF are added thereto, and are warming up to 120 DEG C under nitrogen protection and are reacted 12 hours, and reaction terminates, and are cooled to room temperature, will
Product is poured into deionized water and is extracted, and organic phase extracted is concentrated, crosses column purification, the compound B containing eicosane is made,
Yield is 40%.1H NMR (500 MHz, Chloroform-d) δ 8.89 (d, J = 3.9 Hz, 2H), 7.64
(dd, J = 5.1 Hz, 2H), 7.27 (d, J = 5.1 Hz, 2H), 4.04 (d, J = 7.8 Hz, 4H),
1.93 (s, 2H), 1.58 (s, 4H), 1.37 – 1.20 (m, 60H), 0.86 (q, J = 6.1 Hz, 12H).
Specific implementation method bibliography " Naik, M. A.; Venkatramaiah, N.; Kanimozhi, C.;
Patil, S. J.phys.chem.c2012,116 (50), 26128-26137.》
The synthesis of the presoma C of the unilateral bromine of embodiment 3
2g eicosane compound B is dissolved in 200ml chloroform solvent, and the NBS progress list that equimolar amounts is added dropwise is added at room temperature
Side bromination, every reaction half an hour is tracked with contact plate reacts, until raw material fully reacting, water quenching on the rocks, methylene chloride extraction, mistake
Column purification, obtains the presoma C containing unilateral bromine, yield 50%；1H NMR (500 MHz, Chloroform-d) δ
8.88 (t, J=4.0Hz, 1H), 8.60 (d, J=4.0Hz, 1H), 7.63 (t, J=4.0Hz,1H), 7.27-7.21
(m, 2H), 4.00 (d, J=4.0Hz, 2H), 3.93 (d, J=8.0Hz, 2H), 1.58 (s, 4H), 1.90-
1.89 (m, 2H), 1.36-1.15 (m, 60H), 0.84-0.89 (m, 12H).
Specific implementation method bibliography " Mukhopadhyay, T.; Puttaraju, B.; Senanayak, S. P.;
Sadhanala, A.; Friend, R. H.; Faber, H. A.; Anthopoulos, T. D.; Salzner, U.;
Meyer, A.; Patil, S. Acs Applied Materials & Interfaces 2016,8 (38), 25415.》
The synthesis of embodiment 4 presoma D and E
(a) 1.1g contains compound C, the 0.44g T-SnBu of unilateral bromine3(2- tributylstamlyl thiophene), 53.5mg catalysis
Agent Pd2(dba)3, 35.6mg ligand P (o-Tolyl)3It is dissolved in the Xi Laike pipe for filling 10ml toluene, vacuumizes, inflated with nitrogen three
Secondary circulation, reacts a whole night at 100 DEG C, is cooled to room temperature, be spin-dried for solvent, column is crossed with petroleum ether and methylene chloride, before obtaining
Drive body D, yield 56%.
(b) 0.5g contains compound C, the 0.68g TT-SnBu of unilateral bromine3(" Kawabata K, Takeguchi M,
Goto H . Optical Activity of Heteroaromatic Conjugated Polymer Films Prepared
by Asymmetric Electrochemical Polymerization in Cholesteric Liquid Crystals:
Structural Function for Chiral Induction[J]. Macromolecules, 2013, 46(6):
2078-2091. "), 24.3mg catalyst Pd2(dba)3, 16.13mg ligand P (o-Tolyl)3It is dissolved in and fills 10ml tetrahydrofuran
Xi Laike pipe in, vacuumize, inflated with nitrogen recycles three times, reacts a whole night at 100 DEG C, is cooled to room temperature, be spin-dried for solvent, use
Petroleum ether and methylene chloride cross column, obtain presoma E, yield 59%.
The preparation of embodiment 5 monomer M1-1 and M1-2
(a) 1.1g presoma D is dissolved in 200ml chloroform solvent, and 0.518g NBS is added dropwise at room temperature and carries out both sides bromination, often
It reacts half an hour to be reacted with contact plate tracking, until raw material fully reacting, water quenching on the rocks, methylene chloride extraction is crossed column and purified, obtains
To the presoma M1-1 containing both sides bromine, yield 85%.
(b) 0.2g presoma E is dissolved in 20ml chloroform solvent, and 0.075g NBS is added dropwise at room temperature and carries out both sides bromination, often
It reacts half an hour to be reacted with contact plate tracking, until raw material fully reacting, water quenching on the rocks, methylene chloride extraction is crossed column and purified, obtains
To the presoma M1-2 containing both sides bromine, yield 82%.
The preparation of 6 Polymer of embodiment (one) and Polymer (two)
(a) by 188.71mg monomer M1-1,93.17mg Me3Sn-TT-SnMe3, 3.66 mg catalyst Pd2 (dba)3,
4.87mg ligand P (o-Tolyl)3It is added in the Schlenk pipe of 100ml, 6ml anhydrous chlorobenzene is added.Whole system is at 100 DEG C
Under be stirred to react 12 hours, when system becomes gel, terminate reaction, be cooled to room temperature, some methanol be added and are polymerize
Object precipitating.Methanol is used respectively, and petroleum ether, toluene, the continuous Soxhlet extraction of chloroform 36 hours obtains dry red solid polymer
Polymer (one) 154mg, yield 71%.
(b) by 199.923mg monomer M1-2,81.95mg Me3Sn-T-SnMe3, 3.66 mg catalyst Pd2 (dba)3,
4.87mg ligand P (o-Tolyl)3It is added in the Schlenk pipe of 100ml, 6ml anhydrous chlorobenzene is added.Whole system is at 100 DEG C
Under be stirred to react 36 hours, when system becomes gel, terminate reaction, be cooled to room temperature, some methanol be added and are polymerize
Object precipitating.Methanol is used respectively, and petroleum ether, toluene, the continuous Soxhlet extraction of chloroform 24 hours obtains dry red solid polymer
Polymer (two) 154mg, yield 79%.
Two polymer functional group's characteristic peak having the same is shown in Fig. 7 infrared spectrum.Two polymer are indicated in Fig. 8
Uv atlas under solution state and filminess.Two polymer are under solution, and uv atlas essentially coincides, in film-form
Under state, the absorption peak of polymer (two) is slightly wider than the absorption peak of polymer (one) in 600nm-900nm.It partly leads Fig. 9 is organic
Two polymer are all showing higher mobility in the organic thin film transistor device test of body layer, are all larger than 1 cm2/ (V
S).
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent transformation made by bright specification and accompanying drawing content is applied directly or indirectly in other relevant technical fields, similarly
It is included within the scope of the present invention.
Claims (4)
1. two kinds of asymmetric conjugated polymers in the part containing isomers repetitive unit, which is characterized in that its structural formula are as follows:
With
(1) and in (two) formula R is >=C20Saturation branched alkyl chain, Ar is furans, thiophene or pyridine, n > 0.
2. the preparation side of the two kinds as described in claim 1 asymmetric conjugated polymers in the part containing isomers repetitive unit
Method, which comprises the following steps:
A group: monomer M1-1, Me3Sn-TT –SnMe3, catalyst Pd2(dba)3, ligand P (o-Tolyl)3；
B group: monomer M1-2, Me3Sn-T-SnMe3, catalyst Pd2(dba)3, ligand P (o-Tolyl)3；
Two groups of substances of a and b are dissolved in anhydrous organic solvent respectively, whole system under a nitrogen, is heated to reflux, after polymerization, warp
Cross Soxhlet extraction to be purified, it is respectively Polymer(mono- that vacuum drying, which obtains red solid polymer) and Polymer (two)；
M1-1 the and M1-2 monomer structure are as follows:
R is >=C in M1-1 and M1-220Saturation branched alkyl chain, Ar is pyridine, furans or thiophene.
3. the preparation of two kinds of asymmetric conjugated polymers in the part containing isomers repetitive unit according to claim 2
Method, which is characterized in that the preparation method of the monomer M1-1 and M1-2 includes the following steps:
(1) under alkaline condition by 2- cyano thiophene, 2- cyanopyridine or 2- cyanofuran and diethyl succinate, reaction generates
Compound A, structure are as follows:
Ar is furans, thiophene or pyridine；
(2) by compound A and R >=C20Iodo saturation branched-alkyl chain hydrocarbon obtained by nucleophilic substitution containing alkyl chain
Compound B;
The structure of the compound B containing alkyl chain is as follows:
Wherein R is >=C20Saturation branched alkyl chain, Ar is furans, thiophene or pyridine；
(3) the obtained compound B containing alkyl chain of step (2) is subjected to unilateral bromination with NBS in organic solvent, obtained
Presoma C containing bromine, structure are as follows:
Wherein R is >=C20Saturation branched alkyl chain, Ar is furans, thiophene or pyridine；
(4) the obtained presoma C containing bromine of step (3) coupling reaction is carried out with c group and d group substance respectively to respectively obtain
Presoma D and E；
C group: Bu3Sn-T, catalyst Pd2(dba)3, ligand P (o-Tolyl)3；
D group: Bu3Sn-TT, catalyst Pd2(dba)3, ligand P (o-Tolyl)3；
Wherein R is >=C20Saturation branched alkyl chain, Ar is furans, thiophene or pyridine；
(5) presoma D and E in step (4) are subjected to bromination reaction with NBS respectively, obtain monomer M1-1 and M1-2.
4. two kinds as described in claim 1 containing isomers repetitive unit, locally asymmetric conjugation polymers is organic applied to preparing
On field-effect transistor materials.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150021526A1 (en) * | 2013-07-22 | 2015-01-22 | Xerox Corporation | Semiconductor composition |
| CN106750193A (en) * | 2016-12-12 | 2017-05-31 | 中国科学院化学研究所 | Even tripyrrole and pyrroledione polymer and its synthetic method and application |
-
2019
- 2019-01-09 CN CN201910019408.6A patent/CN109734879A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150021526A1 (en) * | 2013-07-22 | 2015-01-22 | Xerox Corporation | Semiconductor composition |
| CN106750193A (en) * | 2016-12-12 | 2017-05-31 | 中国科学院化学研究所 | Even tripyrrole and pyrroledione polymer and its synthetic method and application |
Non-Patent Citations (1)
| Title |
|---|
| YOO, DOHYUK，ET AL.，: "A Timely Synthetic Tailoring of Biaxially Extended Thienylenevinylene-Like Polymers for Systematic Investigation on Field-Effect Transistors", 《ADVANCED FUNCTIONAL MATERIALS》 * |
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