CN109575244A - A kind of pi-conjugated polymer and preparation method thereof combined containing-NHO=C hydrogen bond action donor-receiver - Google Patents
A kind of pi-conjugated polymer and preparation method thereof combined containing-NHO=C hydrogen bond action donor-receiver Download PDFInfo
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Abstract
The pi-conjugated polymer and preparation method thereof that the present invention relates to a kind of to combine containing-NH ... O=C hydrogen bond action donor-receiver.The present invention passes through radical reaction first and synthesizes a kind of brominated monomer M1, M2, and two monomers are then pressed different proportion and Me3Sn‑TT‑SnMe3Carry out Stille coupling polymerization, the pi-conjugated polymer combined containing-NH ... O=C hydrogen bond action donor-receiver is made using high-temperature heating treatment reaction, contain-NH ... O=C hydrogen bond action in the polymer, intermolecular coplanarity and intermolecular interaction force are improved.The pi-conjugated polymer that should be combined containing-NH ... O=C hydrogen bond action donor-receiver can be dissolved in chlorobenzene, it in the halogenated solvents such as o-dichlorohenzene, can be formed a film by solution-cast, in field effect transistor, with mobility height, good chemical stability.
Description
Technical field
The present invention relates to a kind of pi-conjugated polymer combined containing-NH ... O=C hydrogen bond action donor-receiver and its
Preparation method belongs to field-effect transistor materials field.
Background technique
Organic field effect tube (Organic Field-Effect Transistor, OFET) is basic circuit
Switch element has application in fields such as Electronic Paper, Flexible Displays, microprocessor, chemical/biological sensors.With other
Effect transistor is the same, and the principle of organic field effect tube controls output also with the field effect of control input circuit
Loop current, difference are then, " carrier " transport layer of carry charge is served as using organic semiconducting materials.OFET
Research core be organic semiconducting materials carrier (hole or electronics) mobility.Improving mobility is to study this neck
The target that domain scientist pursues jointly.Organic field effect tube material is generally made of the polymer that donor-receiver combines,
Performance depends on the chemical structure of polymer backbone.A kind of good organic field effect tube material should have preparation letter
It is single, cheap, mobility is high, chemical property stablize the features such as.Reasonable Molecular Design and selection are that high-performance is made
The important prerequisite of organic field effect tube material.
Summary of the invention
The purpose of the invention is to improve the mobility of field effect transistor, one kind is provided and contains-NH ... O=C hydrogen bond
The pi-conjugated polymer and preparation method thereof that the donor-receiver of effect combines.- the NH ... O=C hydrogen bond action polymer
It is simple with preparation process, mobility is high, good chemical stability, scene effect transistor material field have it is huge
Application prospect.
To achieve the above object, the present invention adopts the following technical scheme:
One kind containing-NH ... O=C hydrogen bond action polymer, structural formula are as follows:
；
R is the saturation branched alkyl chain that carbon atom number is equal to greatly 20, m > 0, n > 0 in formula.
Another object of the present invention is to provide a kind of π-combined containing-NH ... O=C hydrogen bond action donor-receiver
The preparation method of conjugated polymer object comprising following steps:
(1) monomer M1, M2, Me3Sn-TT-SnMe3, catalyst Pd2(dba)3, ligand P (o-Tolyl)3Being dissolved in anhydrous halogenated has
It in solvent, under a nitrogen, is heated to reflux, after polymerization, which is purified with Soxhlet extraction, vacuum drying obtains red
Color solid polymer Polymer1；It is described containing M1, M2 monomer structure formula difference is as follows:
Wherein, R is the saturation branched alkyl chain that carbon atom number is equal to greatly 20；
The structural formula of the polymer P olymer1 containing-Boc functional group are as follows:
,
Wherein, R is the saturation branched alkyl chain that carbon atom number is equal to greatly 20, m > 0, n > 0；
It is 4:1,7:1,10:1,40:1 that the proportion of the amount of the substance for the monomer being added in step (1), which is M1:M2,；
(2) by the obtained red solid polymer P olymer1 containing-Boc functional group acquired in step (1) through excessively high
Temperature vacuum drying, the pi-conjugated polymer of the donor-receiver combination for O=C hydrogen bond action that contain-NH ....
The monomer contained M1's the preparation method is as follows:
1) DPP compound A will be contained and halogenated alkane is dissolved in organic solvent, the Anhydrous potassium carbonate of 1.5 times of equivalents of addition-NH
It is activated, is reacted at 100 ~ 130 DEG C 12-24 hours, it is 2 ~ 10 times of organic solvent used that reactant, which is then poured into volume,
Deionized water in, obtained after purification by liquid extraction containing alkyl chain compound B;
The A of compound containing DPP has the following structure:
The compound B containing alkyl chain has the following structure:
Wherein, R is the saturation branched alkyl chain that carbon atom number is equal to greatly 20；
2) the obtained compound B containing alkyl chain of step 1) is subjected to bromination in organic solvent, obtains the list containing bromine
Body M1.
The monomer contained M2's the preparation method is as follows: that DPP compound A 1. will be contained will be molten with 4-dimethylaminopyridine
Solution is added di-tert-butyl dicarbonate (Diboc) in organic solvent, reacts 12 hours at room temperature, it is organic then to remove part
The NaHCO of mass fraction 5% is added in solvent3Solution is filtered, and dissolution is contained the compound C of-Boc after purification;
The compound C containing-Boc has the following structure:
2. by step, 1. the obtained compound C containing-Boc carries out bromination in organic solvent, obtains the monomer containing bromine
M2。
In order to preferably realize that the present invention, above-described one kind contain-NH ... O=C hydrogen bond action donor-receiver
In conjunction with pi-conjugated polymeric oxidizer solvent be chlorobenzene, the halogenating agents such as o-dichlorohenzene.Monomer synthesizes the organic solvent of selection
For DMF, THF, methylene chloride, chloroform equal solvent.
A kind of obtained pi-conjugated polymer combined containing-NH ... O=C hydrogen bond action donor-receiver of the present invention
It can be used for preparing organic field effect tube material.
Remarkable advantage of the invention
(1) raw material of the present invention is common industrial chemicals, cheap, is easy to get, and synthesis technology is simple
Maturation, preparation cost are low；
(2) skeleton selected by the present invention has many advantages, such as the flatness of height, chemical stability；
(3) in the obtained polymer of the present invention containing-NH ... O=C hydrogen bond action, intermolecular coplanarity and intermolecular
Interaction force is improved, and the pi-conjugated polymer that should be combined containing-NH ... O=C hydrogen bond action donor-receiver can
It to be dissolved in chlorobenzene, in the halogenated solvents such as o-dichlorohenzene, can be formed a film by solution-cast, under certain doping, be used for field
In effect transistor, have mobility high, mechanical strength is good, good chemical stability.
Detailed description of the invention
Fig. 1 is the nuclear magnetic resonance spectroscopy of the compound B containing alkyl chain in the embodiment of the present invention 1.
Fig. 2 is the nuclear magnetic resonance spectroscopy of the monomer M1 containing bromine in the embodiment of the present invention 2.
Fig. 3 is the nuclear magnetic resonance spectroscopy of the compound C in the embodiment of the present invention 3 containing-Boc.
Fig. 4 is the nuclear magnetic resonance spectroscopy of the monomer M2 containing bromine in the embodiment of the present invention 4.
Fig. 5 be the embodiment of the present invention 5 in Polymer1(40:1) ultraviolet spectra (behalf solution state, f represent film
State, h-f represent the film after annealing).
Fig. 6 is Polymer1(40:1 in the embodiment of the present invention 5) electrochemical optical spectra (f represents film, and pre-h-f is represented
Film after annealing).
Fig. 7 be the embodiment of the present invention 5 in Polymer1(40:1) device performance (40:1, which represents 40:1 polymer, not to be had
Device performance through overdoping, 40:1:PS represent the device performance after the polymer-doped PS material of 40:1).
Specific embodiment
It is clear in order to which plan content of the present invention is illustrated, in conjunction with specific embodiment to technology of the present invention
Scheme is described further, but technical solution of the present invention is not unique.
The preparation of 1 precursor B of embodiment
3 g(10 mmol) DPP compound A (3,6- Dithiophene -2- base -2,5- pyrrolin simultaneously [3,4-c] pyrroles -1,4- two
Ketone) and 12.25 g (30 mmol) iodo compound (9- (iodomethyl) nonadecane) and 4.5 g (33
Mmol) potassium carbonate is added in the two mouth flask of 250 ml, and 120 ml DMF are added thereto, and is warming up to 120 under nitrogen protection
DEG C reaction 12 hours, reaction terminates, and is cooled to room temperature, and product is poured into 250 ml deionized waters and is extracted, extracted organic
It is mutually concentrated, column purification is crossed, the compound B containing alkyl chain, yield 40% is made.
The preparation of 2 monomer M1 of embodiment
The compound B of 0.43 g (0.5 mmol) containing alkyl chain in embodiment 1 is dissolved in the methylene chloride of 100 ml,
Under ice-water bath, 0.2g(1.1 mmol is added dropwise in nitrogen atmosphere) NBS, it is protected from light a whole night, reaction terminates, and add water to quench,
Methylene chloride extraction, purifies by column, obtains the monomer M1 containing bromine, yield 50%.
The preparation of compound C of the embodiment 3 containing-Boc
1.5g(5 mmol) DPP compound A, 1.28g(10.5mmol) 4-dimethylaminopyridine is dissolved in 50mL THF, in nitrogen
Under, 2.31g(15 mmol is added) Diboc, it reacts at room temperature 12 hours, reaction terminates, and removes partial solvent out, is added 5wt%'s
NaHCO3Solution, filtering, obtains sediment, through drying, crosses column purification, is contained the red solid C of-Boc, yield 30%.
The preparation of 4 monomer M2 of embodiment
0.5 g (1.0 mmol) in embodiment 3 is dissolved in the methylene chloride of 100 ml containing the compound C of-Boc, in nitrogen
Atmosphere is enclosed, and under ice-water bath, 0.44 g(2.5 mmol is added dropwise) NBS, it is protected from light a whole night, reaction terminates, and add water to quench,
Methylene chloride extraction, purifies by column, obtains the monomer M2 containing bromine, yield 80%.
The preparation of polymer P olymer1 of the embodiment 5 containing-Boc functional group
Monomer M2, Me by 2 monomer M1 of embodiment, in embodiment 43Sn-TT-SnMe3, catalyst Pd2(dba)3, ligand P (o-
Tolyl)3It is dissolved in the anhydrous Benzene Chloride of 6ml.Under a nitrogen, temperature is 80 DEG C to whole system, reacts 12 hours.It, will after polymerization
Mixture is cooled to room temperature, and some methanol are added to obtain the precipitating of polymer.Methanol, PE, CHCl is respectively adopted in the polymer3
Soxhlet extraction purified, 80 DEG C of vacuum drying obtain red solid polymer P olymer1.
(1) Polymer1(4:1): 163.1 mg(0.16 mmol) monomer M1,26.34 mg(0.04 mmol) monomer M2,
93.17 mg(0.20 mmol) Me3Sn-TT-SnMe3, the mmol of 3.66 mg(0.20 × 2%) and Pd2(dba)3, 4.87 mg(0.2
× 8% mmol) P (o-Tolyl)3。
(2) Polymer1(7:1): 214.0 mg(0.21 mmol) monomer M1,19.75 mg(0.03 mmol) monomer M2,
111.8 mg(0.24 mmol) Me3Sn-TT-SnMe3, the mmol of 4.39 mg(0.24 × 2%) and Pd2(dba)3, 5.84 mg(0.24
× 8% mmol) P (o-Tolyl)3。
(3) Polymer1(10:1): 203.8 mg(0.20 mmol) monomer M1,13.2 mg(0.02 mmol) monomer M2,
102.5 mg(0.22 mmol) Me3Sn-TT-SnMe3, the mmol of 4.10 mg(0.22 × 2%) and Pd2(dba)3, 5.40 mg(0.22
× 8% mmol) P (o-Tolyl)3。
(4) Polymer1(40:1): 203.8 mg(0.20 mmol) monomer M1,3.30 mg(0.005 mmol) monomer
M2,95.5 mg(0.21 mmol) Me3Sn-TT-SnMe3, the mmol of 3.75 mg(0.21 × 2%) and Pd2(dba)3, 5.0 mg
(0.21 × 8% mmol) P (o-Tolyl)3。
The preparation for the pi-conjugated polymer that embodiment 6 is combined containing-NH ... O=C hydrogen bond action donor-receiver
The obtained red solid polymer P olymer1 containing-Boc functional group is respectively at 220 DEG C in embodiment 5, vacuum
Dry 30 minutes, the pi-conjugated polymer of the donor-receiver combination for O=C hydrogen bond action that contain-NH ....
Embodiment 7 is imitated containing the pi-conjugated polymer that-NH ... O=C hydrogen bond action donor-receiver combines applied to field
It answers in transistor device
The preparation method of device of the present invention is the Polymer1 polymer of 5-15mg to be dissolved in chlorobenzene, in n-octadecane base three
In the silica/silicon substrate of chlorosilane (OTS) modification (highly doped silicon substrate is substrate), the poly- of one layer of 50nm thickness is got rid of
Object film is closed, golden source-drain electrode is deposited above with mask plate in organic film, so that the OFET device of top electrode structure be made.It will
Polymer1 thin polymer film is in 240 DEG C of annealing (donor-receiver knots for O=C hydrogen bond action that contained-NH after annealing ...
The pi-conjugated polymer closed).Wherein Polymer1(40:1) the maximum electron mobility that measures reaches 1.5cm2/ (V s), is opened
It closes than being 107。
As can be seen from Figure 5 polyme1(40:1) thin polymer film and annealing after film relative to its solution state
Blue shift has occurred.
As can be seen from Figure 6 polyme1(40:1) all only apparent oxidation of film after thin polymer film and annealing
Peak, without reduction peak.
From Fig. 7, it can be found that 40:1 device is high relative to the device mobility of 40:1:PS, hysteresis effect is small.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (8)
1. the pi-conjugated polymer that one kind is combined containing-NH ... O=C hydrogen bond action donor-receiver, which is characterized in that it is tied
Structure formula are as follows:
；
R is the saturation branched alkyl chain that carbon atom number is equal to greatly 20, m > 0, n > 0 in formula.
2. a kind of pi-conjugated polymerization combined containing-NH ... O=C hydrogen bond action donor-receiver as described in claim 1
The preparation method of object, which comprises the following steps:
(1) monomer M1, M2, Me3Sn-TT-SnMe3, catalyst Pd2(dba)3, ligand P (o-Tolyl)3Being dissolved in anhydrous halogenated has
In solvent, whole system under a nitrogen, is heated to reflux, and after polymerization, is purified by Soxhlet extraction, and vacuum drying obtains red
Color solid polymer Polymer1, the M1 monomer structure formula are as follows:
,
Wherein, R is the saturation branched alkyl chain that carbon atom number is equal to greatly 20；
The M2 monomer structure formula are as follows:
；
The structural formula of the red solid polymer P olymer1 containing-Boc functional group are as follows:
,
Wherein, R is the saturation branched alkyl chain that carbon atom number is equal to greatly 20, m > 0, n > 0；
(2) by the red solid polymer P olymer1 containing-Boc functional group obtained in step (1) vacuum at high temperature
It is dry, the pi-conjugated polymer of the donor-receiver combination for O=C hydrogen bond action that contain-NH ....
3. the pi-conjugated polymer combined according to claim 2 containing-NH ... O=C hydrogen bond action donor-receiver
Preparation method, which is characterized in that the anhydrous halogenated organic solvent be chlorobenzene or o-dichlorohenzene.
4. the pi-conjugated polymer combined according to claim 2 containing-NH ... O=C hydrogen bond action donor-receiver
Preparation method, which is characterized in that step (1) be added monomer M1 and M2 the mass ratio of the material be 4:1,7:1,10:1,40:1
Or 100:0.
5. the pi-conjugated polymer combined according to claim 2 containing-NH ... O=C hydrogen bond action donor-receiver
Preparation method, which is characterized in that the preparation method of the monomer M1 the following steps are included:
1) DPP compound A will be contained and halogenated alkane is dissolved in organic solvent, the Anhydrous potassium carbonate of 1.5 times of equivalents of addition-NH
It is activated, is heated to reflux, after reaction, it is 2 ~ 10 times of organic solvent of deionized water used that reactant, which is poured into volume,
In, the compound B containing alkyl chain is obtained after purification by liquid extraction;
The structural formula of the A of compound containing DPP are as follows:
The structural formula of the compound B containing alkyl chain are as follows:
,
Wherein, R is the saturation branched alkyl chain that carbon atom number is equal to greatly 20；
2) by the obtained compound B containing alkyl chain of step 1), bromination is carried out in organic solvent, obtains the list containing bromine
Body M1.
6. the pi-conjugated polymer combined according to claim 5 containing-NH ... O=C hydrogen bond action donor-receiver
Preparation method, which is characterized in that the preparation method of the monomer M2 the following steps are included:
1. DPP compound A will be contained and 4-dimethylaminopyridine is dissolved in organic solvent, di-tert-butyl dicarbonate is added, in room
Temperature lower reaction 12 hours, part organic solvent is then removed, the NaHCO of mass fraction 5% is added3Solution is filtered, and dissolution mentions
Contained the compound C of-Boc after pure;
The structural formula of the compound C containing-Boc are as follows:
；
2. by step, 1. the obtained compound C containing-Boc carries out bromination in organic solvent, obtains the monomer containing bromine
M2。
7. containing the pi-conjugated poly- of-NH ... O=C hydrogen bond action donor-receiver combination according to claim 5 or 6
Close the preparation method of object, which is characterized in that the organic solvent is DMF, THF, methylene chloride or chloroform.
8. a kind of pi-conjugated polymerization combined as described in claim 1 containing-NH ... O=C hydrogen bond action donor-receiver
Object is applied to prepare on organic field effect tube material.
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| CN112646128A (en) * | 2020-12-07 | 2021-04-13 | 广东聚华印刷显示技术有限公司 | Polymer material, preparation method thereof, electronic device containing polymer material and display equipment |
| CN113354797A (en) * | 2021-04-29 | 2021-09-07 | 深圳大学 | Method for preparing thermoelectric material by using polymer containing removable side chain and thermoelectric material |
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| CN112646128B (en) * | 2020-12-07 | 2023-11-03 | 广东聚华印刷显示技术有限公司 | Polymer material, preparation method thereof, electronic device and display equipment containing polymer material |
| CN113354797A (en) * | 2021-04-29 | 2021-09-07 | 深圳大学 | Method for preparing thermoelectric material by using polymer containing removable side chain and thermoelectric material |
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