CN109651601B - Novel hydrogen bond crosslinking stretchable conductive polymer and synthesis method thereof - Google Patents

Novel hydrogen bond crosslinking stretchable conductive polymer and synthesis method thereof Download PDF

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CN109651601B
CN109651601B CN201811466213.8A CN201811466213A CN109651601B CN 109651601 B CN109651601 B CN 109651601B CN 201811466213 A CN201811466213 A CN 201811466213A CN 109651601 B CN109651601 B CN 109651601B
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卢宝阳
屈凯
徐景坤
刘西梅
陈帅
渐南南
朱秀凯
胡法琪
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Hefei Longzhiyun Pharmaceutical Technology Co ltd
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    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
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Abstract

The invention discloses a novel hydrogen bond crosslinking stretchable conductive polymer and a synthesis method thereof, belonging to the technical field of polymer synthesis. The novel hydrogen bond crosslinking stretchable conductive polymer comprises hydrogen bond crosslinking stretchable groups and functional conductive groups; the hydrogen bond crosslinking stretchable group is a nitrogen-containing heterocyclic ring; the functional conducting group is oligomers of 3, 4-Ethylenedioxythiophene (EDOT), thiophene, selenophene and pyrrole and derivatives thereof. The novel hydrogen bond crosslinking stretchable conductive polymer prepared by the invention is based on an intrinsic stretchable group as a core, so that the polymer has good stretchable self-healing performance.

Description

Novel hydrogen bond crosslinking stretchable conductive polymer and synthesis method thereof
Technical Field
The invention relates to the technical field of polymer synthesis, in particular to a novel hydrogen bond crosslinking stretchable conductive polymer and a synthesis method thereof.
Background
Since the first discovery in 1976 that Polyacetylene (PA) after doping has metal-like conductivity, people have made a new cross discipline of conductive polymers with a continuous deepening and improvement on the structure and understanding of conjugated polymers. In subsequent studies, conductive polymers such as polypyrrole, polyparaphenylene, polyphenylene sulfide, polythiophene, polyaniline and the like are gradually found. The special structure and excellent physical and chemical properties of the conductive polymer make the conductive polymer become a research hotspot of material science, and as one of the irreplaceable new basic organic functional materials, the conductive polymer material has wide application prospects in energy sources, photoelectronic devices, information, sensors, molecular leads, molecular devices, electromagnetic shielding, metal corrosion prevention and stealth technologies. So far, the research on the application and exploration of the conductive polymer in molecular design and material synthesis, doping method and mechanism, solubility and processability, conductive mechanism, optical, electrical, magnetic and other physical properties, related mechanisms and technologies have all made important research progress.
The research on the non-covalent cross-linking of hydrogen bonds among conjugated polymer chains has made a breakthrough and becomes an effective method for realizing high stretching and self-healing of the conductive polymer. The formation of hydrogen bonds is mainly due to electrostatic forces, the bond energy of which is mostly 25-40kJ/mol, slightly stronger than van der Waals forces, but the forces and stability are significantly weaker than covalent and ionic bonds. In polymer science, hydrogen bonds are easily rearranged among polymer chains, so that the polymer has a self-healing function. Recent studies have found that the number of building blocks for organic semiconductors far exceeds theoretical analysis and prediction, and in particular, the research groups such as glowecki have surprisingly found that carriers can be transported efficiently in materials containing intermolecular hydrogen bonds. In 2016, a teaching and research group in Baozhinan introduces intermolecular hydrogen bonds into a conjugated polymer structure, and prepares a novel intrinsic stretchable and self-healing polymer semiconductor by regulating and controlling the proportion of a rigid conjugated structural unit and a hydrogen bond crosslinking flexible carbon chain in a material, and the novel intrinsic stretchable and self-healing polymer semiconductor is used for manufacturing a stretchable field effect transistor.
Disclosure of Invention
The invention aims to provide a novel hydrogen bond crosslinking stretchable conductive polymer and a synthesis method thereof, wherein the polymer is composed of a hydrogen bond crosslinking stretchable group and a conjugated conductive group, and the hydrogen bonds between polymer chains are non-covalently crosslinked, so that the polymer has a self-healing function while having high conductive performance.
In order to solve the technical problems, the invention provides the following technical scheme:
the hydrogen bond crosslinking stretchable group mainly adopts a nitrogen-containing heterocyclic compound, and a series of excellent flexible stretchable multi-hydrogen bond bonding units are built by controlling or pre-organizing hydrogen bond sites through the rigidity of the nitrogen-containing heterocyclic ring and hydrogen bonds in a structural molecule. The conjugated unit of the functional conducting group has high crystallinity (crystal region) and can realize charge transmission of materials. And carrying out still coupling reaction or Suzuki coupling reaction on the functional conducting group and the flexible group to obtain the hydrogen bond crosslinked intrinsic stretchable flexible conducting polymer material. The simultaneous existence of the hydrogen bond crosslinking stretchable group and the functional conductive group enables the polymer to realize the stretchable performance while having high conductivity.
The invention provides a novel hydrogen bond crosslinking stretchable conductive polymer, which comprises a hydrogen bond crosslinking stretchable group and a functional conductive group;
the hydrogen bond crosslinking stretchable group is a nitrogen-containing heterocyclic ring;
the functional conducting group is oligomers of 3, 4-Ethylenedioxythiophene (EDOT), thiophene, selenophene and pyrrole and derivatives thereof.
Further, the nitrogen-containing heterocyclic ring is a heterocyclic ring parent modified by amide, diacetyl amide or imide, and a conjugated bond is provided at the tail end by thiophene and EDOT.
Preferably, the hydrogen-bond crosslinking stretchable group is:
Figure BDA0001889873440000031
any one of the above;
wherein X is S, Se or O atom;
R1is a hydrogen atom or a methyl group;
R2is an atom, C1～12Straight chain alkyl group of (1), C1～12Straight-chain alkyl with side chain, C1～12A straight or branched alkoxy group, a fluorine atom or a chlorine atom.
Further, the structural formula of the functional conducting group is as follows:
Figure BDA0001889873440000032
wherein n is more than or equal to 1;
x is sulfur, nitrogen, selenium or oxygen;
r is a hydrogen atom, C1～12Straight chain alkyl group of (1), C1～12Straight-chain alkyl with side chain, C1～12And n is 1, 2, 3,4, 5, 6 or 8 respectively.
Further, the structural formula of the functional conducting group is as follows:
Figure BDA0001889873440000041
wherein X is sulfur, selenium or oxygen;
r is hydrogen, C1～12Straight chain alkyl group of (1), C1～12Straight-chain alkyl with side chain, C1～12Straight or branched alkoxy, fluorine or chlorine;
n1is 1-8, n2Is 0 to 4.
Preferably, said C1～12The straight-chain alkyl with a side chain is 2-methylpropane, 2-methylhexane, 2-ethylhexane, 2-ethylheptane, 2-hexyloctane, 2-octyldecyl, 2-octyldodecyl, 2-decyldodecyl or 2-decyltetradecyl.
The invention also provides a synthesis method of the novel hydrogen bond crosslinking stretchable conductive polymer, which comprises the following steps:
step 1: synthesizing tin-butylated, hydrogen-bonded, stretchable groups;
step 2: synthesizing a brominated functional conductive group;
and step 3: synthesizing tin butylated functional conducting groups;
and 4, step 4: and (3) carrying out Stille coupling reaction or Suzuki coupling reaction on the product synthesized in the step (1-3) to obtain the novel hydrogen bond crosslinking stretchable conductive polymer material.
Further, the tin butylated hydrogen bonded stretchable group: tin-butylated functional conductive group: the mass ratio of the brominated functional conductive groups is 0.1-1.9: 0.1-1.9: 2.
the invention adopts the following synthetic strategy: the preparation method comprises the steps of taking a tin-butylated hydrogen bond crosslinking stretchable group and a brominated functional conducting group of a five-membered heterocyclic or aromatic structure as raw materials, carrying out palladium-catalyzed cross-coupling reaction in a solvent to obtain a hydrogen bond crosslinking intrinsic stretchable conducting polymer in one step, and controlling the stretchable performance of the stretchable polymer by adjusting different feed ratios.
The synthesis route is specifically as follows:
Figure BDA0001889873440000051
wherein the catalyst is palladium tetratriphenylphosphine Pd (PPh) as described above3)4Or bis-triphenylphosphine palladium dichloride Pd (PPh)3)2Cl2(ii) a The solvent is one or more of Tetrahydrofuran (THF), toluene, and N, N-Dimethylformamide (DMF).
Compared with the prior art, the invention has the following beneficial effects:
(1) the hydrogen bond crosslinking intrinsic stretchable conductive polymer material is based on an intrinsic stretchable group as a core, so that the polymer has good stretchable self-healing performance, and certain theoretical guidance, material and technical support are provided in the field of intrinsic stretchable conductive polymers.
(2) The existence of the group with the pi bond conjugated system and the flexible stretchable group enables the polymer to have high conductivity, and simultaneously, the polymer with high molecular weight and stretchable performance is prepared, the reaction condition is mild, and the preparation method is suitable for industrial production and has good application prospect.
(3) The hydrogen bond crosslinking intrinsic stretchable conductive polymer material is obtained through chemical polymerization, compared with a polymer obtained through electrochemical polymerization, the polymer theoretically has smaller structural defects, the polymer is spin-coated on a stretchable substrate through a spin coating method, is soaked in anhydrous dichloromethane or acetonitrile, monomers on the surface of a film and some polymers with lower polymerization degrees are washed away, and then the film is dried in a vacuum box. The intrinsic stretchable conductive electrode can be obtained, and the electrode can be applied to various flexible electronic devices and provides great theoretical guidance and technical support for the field of electronic devices.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of the compound N2, N6-bis (2- (thien-2-yl) ethyl) pyridine-2, 6-dicarboxamide (PDCA) of example 1 of the present invention;
FIG. 2 shows the compound N2, N6-bis (2- (5- (tributylstannyl) thiophen-2-yl) ethyl) pyridine-2, 6-dicarboxamide (SnBu) according to example 1 of the present invention3-PDCA-SnBu3) Nuclear magnetic hydrogen spectrum;
FIG. 3 is a nuclear magnetic hydrogen spectrum of 5, 7-dibromo-3, 4-dioxyethylene thiophene (Br-EDOT-Br) of example 1 according to the present invention;
FIG. 4 is a nuclear magnetic hydrogen spectrum of Tri (3, 4-ethylenedioxythiophene) (TriEDOT) which is a compound of example 1 of the present invention;
FIG. 5 shows the compound 3, 4-dioxotrimethylene- (dibutyl) thiophene (ProDOT-Bu) of example 2 of the present invention2) Nuclear magnetic hydrogen spectrum;
FIG. 6 shows the compound Bis (3, 4-dioxopropylene- (dibutyl) thiophene) (BisProDOT-Bu) of example 2 according to the present invention2) Nuclear magnetic hydrogen spectrum;
FIG. 7 shows the compound Snbutyl-Bis (3, 4-dioxotrimethylene- (dibutyl) thiophene) -Snbutyl (SnBu) in example 2 of the present invention3-BisProEDOT-Bu2-SnBu3) Nuclear magnetic hydrogen spectrum diagram
FIG. 8 is a picture of a SEBS substrate before and after spin coating;
FIG. 9 is a view showing the state before and after stretching of the stretchable conductive polymer of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description will be given with reference to specific embodiments and drawings, but the present invention is by no means limited to these examples. The following description is only a preferred embodiment of the present invention, and is only for the purpose of explaining the present invention, and should not be construed as limiting the scope of the present invention. It should be understood that any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
The components used in the present invention are all commercially available products unless otherwise specified.
The invention provides a novel hydrogen bond crosslinking stretchable conductive polymer and a synthesis method thereof, and the specific implementation mode is as follows.
Example 1
A hydrogen bond crosslinking intrinsic stretchable conductive polymer based on EDOT oligomer is prepared by the following steps:
(1) synthesis of the stretchable group N2, N6-bis (2- (5- (tributyltin) thiophene) ethyl) pyridine-2, 6-dicarboxamide (SnBu)3-PDCA-SnBu3)：
Figure BDA0001889873440000071
1a) Dissolving 2, 6-pyridinedicarboxylic acid (5.00g, 30mmol) as a raw material, dropwise adding oxalyl chloride (11.43g, 90mmol) at 0 ℃, heating the solution to 25 ℃ after dropwise adding, and stirring to react to generate 2, 6-pyridinedicarboxylic acid dichloride with the yield of 95%;
1b) the resulting 2, 6-pyridinedicarboxylic acid dichloride (6.00g, 360mmol) and 2-thienylethylamine (12.00g, 640mmol) were dissolved in triethylamine (5mL) and CH2Cl2Reacting in the mixed solution (40mL) at room temperature to generate N2, N6-bis (2- (thiophene-2-yl) ethyl) pyridine-2, 6-dicarboxamide (PDCA), and separating and purifying by using a silica gel chromatographic column to obtain a white solid.
The result of the nuclear magnetic spectrum detection of the white solid is shown in figure 1: 1H NMR (400MHz, CDCl3) Δ 8.33(d,2H),8.16(s,2H),8.01(t,1H),7.12(d,2H), 6.99-6.85 (m,2H),6.82(s,2H),3.70(q,4H),3.12(t, 4H); the yield was 82%.
1c) Completely dissolving PDCA short chain (1.0g, 2.61mmol) in refined THF, cooling to-78 deg.C, dropwise adding n-BuLi (13.00mL, 20.80mmol) under nitrogen atmosphere, stirring at low temperature for reaction for 2h, dropwise adding tributyltin chloride (7.20g, 22.1mmol) for reaction for 8h, distilling under reduced pressure to remove solvent after reaction is completed,purifying and separating with silica gel chromatographic column treated with triethylamine to obtain white solid (SnBu)3-PDCA-SnBu3)。
Nuclear magnetic hydrogen spectroscopy figure 2, 1H NMR (400MHz, CDCl3) δ 8.35(d,1H),8.03(t,1H),7.81(t,1H),6.98(d,2H),3.76(q,2H),3.22(t,2H), 1.65-1.40 (m,7H), 1.40-1.20 (m,8H), 1.12-0.99 (m,6H),0.86(t,10H), 45% yield.
(2) Synthesis of compound SnBu3-Tri (3, 4-ethylenedioxythiophene) -SnBu3(SnBu3-TriEDOT-SnBu3)：
Figure BDA0001889873440000081
2a) EDOT (1.00g, 7.02mmol) was dissolved homogeneously in chloroform (50mL) and glacial acetic acid (1mL) at room temperature, NBS (0.72g, 4.04mmol) was added to the solution at room temperature, the reaction was stirred for 12h, TLC detected, and after completion of the reaction CH was washed with water2Cl2Extracting, combining organic phases, drying for 24h by anhydrous magnesium sulfate, removing the solvent by reduced pressure distillation, and purifying and separating by using a silica gel chromatographic column treated by triethylamine to obtain a white solid (Br-EDOT-Br).
Nuclear magnetic hydrogen spectrum fig. 3: 1H NMR (400MHz, CDCl3) delta 4.27(s, 1H); the yield was 87%.
2b) Evenly dissolving EDOT (1.50g, 10.71mmol) in THF, cooling to-78 ℃, dropwise adding n-BuLi under nitrogen atmosphere, reacting for two hours, dropwise adding tributyltin chloride (2.05g, 6.3mmol), heating to-48 ℃, reacting for 8 hours, and generating tin-butylated EDOT (EDOT-SnBu)3)。
Nuclear magnetic hydrogen spectrum diagram 4: 1H NMR (400MHz in CDCl 3). delta.6.27 (s,2H), 4.49-4.27 (m,8H),4.24(d, 4H).
2c) Under the protection of nitrogen, 5, 7-dibromo-3, 4-dioxyethylene thiophene and 5-stannyl-3, 4-dioxyethylene thiophene in certain proportion are added into a three-neck flask containing a toluene solvent, and the mixture is added into a catalyst Pd (PPh)3)4Carrying out condensation reflux reaction for 12h at 110 ℃ under catalysis; after the reaction is finished, washing the product with water, extracting with trichloromethane, drying for 24h with a small amount of anhydrous magnesium sulfate,then, the solvent is removed by reduced pressure distillation, and the mixture is purified and separated by a silica gel chromatographic column to obtain a light yellow solid product TriEDOT with the yield of 58 percent.
2d) Evenly dissolving TriEDOT (2.00g, 4.76mmol) in THF, cooling to-78 ℃, dropwise adding n-BuLi (17.8mL, 28.57mmol) under nitrogen atmosphere, reacting for two hours, dropwise adding tributyltin chloride (9.43g, 29.00mmol), heating to-48 ℃, reacting for 8 hours to generate tin-butylated EDOT (SnBu)3-TriEDOT-SnBu3) The yield was 41%.
(3) Synthesis of stretchable conductive polymers based on EDOT oligomers:
Figure BDA0001889873440000091
3a) under the protection of nitrogen, adding SnBu into a three-neck flask containing toluene solvent in sequence3-triEDOT-SnBu3，②SnBu3-PDCA-SnBu3(iii) Br-EDOT-Br in a proportion (1: 2: 1.9:0.1:2, 1.5:0.5:2, 1:1:2, 0.5:1.5:2, 0.1:1.9:2) over Pd (PPh) catalyst3)4Condensing and refluxing for 24 hours at 110 ℃ under catalysis; and after the reaction is finished, washing the product with water, extracting with dichloromethane, drying a small amount of anhydrous magnesium sulfate for 24 hours, then distilling under reduced pressure to remove the solvent to obtain a black solid, dissolving the solid in chloroform, recrystallizing the obtained polymer in n-hexane, petroleum ether and methanol respectively, and filtering to obtain a filter cake. The resulting polymer was subjected to soxhlet extraction in methanol and acetone, respectively, for 24h to recover the polymer solids, to obtain a stretchable conductive polymer based on EDOT oligomer.
Example 2
Based on ProDOT-Bu2A hydrogen-bonded crosslinked intrinsically stretchable conductive polymer of an oligomer prepared by the steps of:
(1) synthesis of the stretchable group N5, N5' bis (2- (2, 2' - (tributyltin) -thiophene) ethyl) - [2,2' -bipyridine]-5,5' -dicarboxamide (SnBu)3-BPDCA-SnBu3)：
Figure BDA0001889873440000092
1a) 2,2 '-bipyridine 5,5' -dicarboxylic acid (1.00g, 4.10mmol) was suspended in thionyl chloride (20mL) at room temperature, and several drops of Dimethylformamide (DMF) were added to the above suspension, which then became a clear red solution. The solution was continuously stirred for several hours, and then thionyl chloride was distilled off under reduced pressure. The pale yellow solid remaining in the flask was washed several times with cold dichloromethane to give the product 2,2 '-bipyridine 5,5' -dicarboxylic acid dichloride (BPYDC).
1b) The resulting 2,2 '-bipyridine 5,5' -dicarboxylic chloride (5.00g, 17.80mmol) and 2-thienylethylamine (5.65g, 44.5mmol) were dissolved in triethylamine (8mL) and CH2Cl2Reacting the mixture (60mL) at room temperature for 12 hours to generate N5, N5 'bis (2-thiophen-2-yl) ethyl) - [2,2' -bipyridine]5,5' -dicarboxamide (BPDCA), and separating and purifying by a silica gel column chromatography to obtain a yellow solid with the yield of 52%;
1c) completely dissolving BPDCA short chain (1.0g, 2.16mmol) in refined THF, cooling to-78 deg.C, dropwise adding n-BuLi (13.00mL, 20.80mmol) under nitrogen atmosphere, stirring at low temperature for 2 hr, dropwise adding tributyl tin chloride (7.20g, 22.1mmol) for reaction for 8 hr, distilling under reduced pressure to remove solvent, purifying with triethylamine-treated silica gel chromatography column to obtain white solid (SnBu)3-BPDCA-SnBu3) The yield was 45%.
(2) Synthesis of the Compound TINOBUTYL-BIS (3, 4-DIOXOPROPYLENE- (DIBUTYL) THIOPHENE) -TINOBUTYL (SnBu)3-BisProEDOT-Bu2-SnBu3)：
Figure BDA0001889873440000101
2a) Dissolving 3, 4-dimethoxythiophene (1.00g, 6.94mmol) and 2, 2-dibutyl-1, 3-propanediol (1.57g, 8.33mmol) in 50mL of toluene, adding p-toluenesulfonic acid (0.02g) under the protection of nitrogen, heating in an oil bath at 110 ℃, refluxing and stirring for 16h until the reaction is complete; the obtained product is used in twoExtracting with chloromethane, standing, mixing organic phases, washing with saturated saline solution, adding anhydrous magnesium sulfate into the obtained organic phase, drying for 24h, vacuum filtering, rotary steaming to obtain solid, purifying with silica gel column chromatography to obtain colorless liquid 3, 4-dioxy propylene- (dibutyl) thiophene (ProDOT-Bu)2)。
Nuclear magnetic hydrogen spectrum fig. 6: 1H NMR (400MHz, CDCl3) Δ 6.41(s,2H),3.85(s,4H), 1.43-1.34 (m,5H), 1.34-1.28 (m,5H),0.92(t, 8H); the yield was 85%.
2b) ProDOT-Bu2(1.00g, 3.73mmol), Tetramethylethylenediamine (TMEDA) (0.87g, 7.46mmol) were dissolved in THF (50mL), after cooling to-78 deg.C a solution of n-BuLi (0.29g, 4.48mmol) in hexane was added under a nitrogen atmosphere, stirring for 30 minutes, after which the solution was transferred to a solution of ferric acetylacetonate in THF, passed through a cannula under nitrogen and the reaction mixture refluxed overnight. Removing volatile in vacuum, purifying with silica gel chromatographic column to obtain colorless oily liquid Bis (3, 4-dioxy propylene- (dibutyl) thiophene) (BisProDOT-Bu)2)。
Nuclear magnetic hydrogen spectrum fig. 7: 1H NMR (400MHz in CDCl3) delta 6.34(s,2H),3.93(s,4H),3.84(s,4H), 1.46-1.40 (m,6H), 1.37-1.21 (m,18H),0.92(s,12H), 53% yield.
2c) BisProDOT-Bu2(1.20g, 1.07mmol) is uniformly dissolved in THF, the solution is cooled to-78 ℃, n-BuLi (2.68mL, 4.28mmol) is added dropwise under the nitrogen atmosphere, tributyltin chloride (1.46g, 4.50mmol) is added dropwise after the reaction is carried out for two hours, the reaction is carried out for 8 hours after the temperature is raised to-48 ℃, the solvent is removed by reduced pressure distillation, and a silica gel chromatographic column treated by triethylamine is used for purification and separation to obtain colorless liquid, thus generating the stannylated BisProDOT-Bu2(SnBu3-BisProDOT-Bu2-SnBu3)。
Nuclear magnetic hydrogen spectrum fig. 8: 1H NMR (400MHz, CDCl3), delta 3.89(s,4H),3.73(s,4H),1.46(d,24H), 1.33-1.28 (m,37H), 0.85-0.70 (m,30H), 87% yield.
(3) The synthesis is based on ProDOT-Bu2Stretchable conductive polymer of oligomer:
Figure BDA0001889873440000111
3a) under the protection of nitrogen, adding SnBu into a three-neck flask containing toluene solvent in sequence3-BisProDOT-Bu2-SnBu3，②SnBu3-BPDCA-SnBu3，③Br-ProDOT-Bu2-Br in a ratio (r: c: 1.9:0.1:2, 1.5:0.5:2, 1:1:2, 0.5:1.5:2, 0.1:1.9:2) over catalyst Pd (PPh)3)4Condensing and refluxing for 24 hours at 110 ℃ under catalysis; and after the reaction is finished, washing the product with water, extracting with dichloromethane, drying a small amount of anhydrous magnesium sulfate for 24 hours, then distilling under reduced pressure to remove the solvent to obtain a black solid, dissolving the solid in chloroform, recrystallizing the obtained polymer in n-hexane, petroleum ether and methanol respectively, and filtering to obtain a filter cake. The resulting polymer was subjected to soxhlet extraction in methanol and acetone, respectively, for 24h to recover the polymer solids, to obtain a stretchable conductive polymer based on EDOT oligomer.
The properties of the novel hydrogen bond-crosslinked stretchable conductive polymer prepared in the above example were tested as follows.
Firstly, manufacturing and surface activation of an SEBS substrate: 200mg/ml SEBS toluene solution, stirring for 20min, vacuum degassing for 10min, and dripping onto 3 × 3cm2Curing the glass plate for 15min at 70 ℃; then activating the surface of the ultraviolet-ozone cleaning machine for 30min at the temperature of about 50-70 ℃ to reduce the surface hydrophobicity. Spin coating: spin coating (1000rpm,1min) the prepared toluene solution (0.5mol/L) of the polymer of example 1 on the prepared SEBS substrate, and annealing for 25min to obtain the stretchable conductive substrate.
And (3) conductivity test: copper wires were attached to both ends of the spin-coated polymer substrate using silver paste, and the conductivity of the polymer during stretching was measured using the four-electrode method, the results of which are shown in table 1. Recovering after releasing the tension: after releasing the tension, a small amount of organic solvent (toluene solution) was sprayed on the substrate, and after drying, the conductivity of the stretched film was recovered, and the results are shown in table 1.
TABLE 1
Draw ratio Long (mm) Width (mm) Thickness (nm) Conductivity (S/cm)
0％ 8 5.1 700 16.13
50％ 12 4.8 700 14.66
100％ 16 3.8 700 7.06
150％ 20 3.4 700 3.35
200％ 24 3.0 700 2.59
250％ 28 2.8 700 2.38
Recovery 8 5.1 700 11.36
As can be seen from Table 1, after 50% stretching, the conductivity is hardly reduced, and after 250% stretching recovery, the conductivity of the conductive polymer is recovered to 11.36S/cm, which still meets the use conditions, thus proving that the novel hydrogen bond crosslinking stretchable conductive polymer prepared by the invention has good stretchable self-healing performance.
In conclusion, the novel hydrogen bond crosslinking stretchable conductive polymer and the synthesis method thereof have good stretchable self-healing performance based on the intrinsic stretchable group as the core.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (5)

1. A hydrogen bond crosslinked stretchable conductive polymer comprising hydrogen bond crosslinked stretchable groups and functional conductive groups;
the functional conducting group is oligomers of 3, 4-Ethylenedioxythiophene (EDOT), thiophene, selenophene and pyrrole and derivatives thereof;
the hydrogen bond crosslinking stretchable group is:
Figure FDA0003034804430000011
any one of the above;
wherein X is S, Se or O atom;
R1is a hydrogen atom or a methyl group;
R2is C1～12Straight chain alkyl group of (1), C1～12Straight-chain alkyl with side chain, C1～12A straight or branched alkoxy group of (a), a fluorine atom or a chlorine atom;
the structural formula of the functional conductive group is as follows:
Figure FDA0003034804430000021
wherein n is more than or equal to 1;
x is sulfur, selenium or oxygen;
r is a hydrogen atom, C1～12Straight chain alkyl group of (1), C1～12Straight-chain alkyl with side chain, C1～12N is 1, 2, 3,4, 5, 6, 8 respectively;
or, the functional conductive group has a structural formula:
Figure FDA0003034804430000022
wherein X is sulfur, selenium or oxygen;
r is hydrogen, C1～12Straight chain alkyl group of (1), C1～12Straight-chain alkyl with side chain, C1～12Straight or branched alkoxy, fluorine or chlorine;
n1is 1-8, n2Is 0 to 4;
the synthesis method of the hydrogen bond crosslinking stretchable conductive polymer comprises the following steps:
step 1: synthesizing tin-butylated, hydrogen-bonded, stretchable groups;
step 2: synthesizing a brominated functional conductive group;
and step 3: synthesizing tin butylated functional conducting groups;
and 4, step 4: and (3) performing Stille coupling reaction on the product synthesized in the step (1-3) to obtain the hydrogen bond crosslinking stretchable conductive polymer material.
2. The hydrogen-bond crosslinked stretchable conductive polymer of claim 1, wherein the C is1～12The straight-chain alkyl with a side chain is 2-methylpropane, 2-methylhexane, 2-ethylhexane or 2-ethylheptane.
3. The hydrogen bond crosslinked stretchable conductive polymer of claim 1, characterized in that the tin butylated hydrogen bond crosslinked stretchable group: tin-butylated functional conductive group: the mass ratio of the brominated functional conductive groups is 0.1-1.9: 0.1-1.9: 2.
4. the hydrogen bond-crosslinked stretchable conductive polymer according to claim 3, characterized by being prepared by the steps of:
(1) synthesis of the stretchable group SnBu3-PDCA-SnBu3：
1a) Dissolving 30mmol of 2, 6-pyridinedicarboxylic acid, dripping 90mmol of oxalyl chloride at 0 ℃, heating the solution to 25 ℃ after dripping is finished, and stirring to react to generate 2, 6-pyridinedicarboxylic acid dichloride;
1b) dissolving the generated 360mmol of 2, 6-pyridine diformyl chloride and 640mmol of 2-thiophene ethylamine in 5mL of triethylamine and CH2Cl2Reacting at room temperature in 40mL of mixed solution to generate PDCA, and separating and purifying by using a silica gel layer chromatographic column to obtain white solid;
1c) completely dissolving PDCA2.61mmol in refined THF, cooling to-78 deg.C, dropwise adding n-BuLi 20.80mmol under nitrogen atmosphere, stirring at low temperature, and reactingDropwise adding 22.1mmol of tributyltin chloride for reacting for 8h within 2h, after the reaction is completed, distilling under reduced pressure to remove the solvent, and purifying and separating by using a silica gel chromatographic column treated by triethylamine to obtain white solid SnBu3-PDCA-SnBu3；
(2) Synthesis of compound SnBu3-TriEDOT-SnBu3：
2a) Dissolving EDOT7.02mmol in chloroform 50mL and glacial acetic acid 1mL at room temperature, adding NBS 4.04mmol into the solution at room temperature, stirring for reaction for 12h, detecting by TLC, washing CH with water after reaction is completed2Cl2Extracting, combining organic phases, drying for 24 hours by using anhydrous magnesium sulfate, removing the solvent by using reduced pressure distillation, and purifying and separating by using a silica gel chromatographic column treated by triethylamine to obtain white solid Br-EDOT-Br;
2b) evenly dissolving 10.71mmol of EDOT in THF, cooling to-78 ℃, dropwise adding n-BuLi under the atmosphere of nitrogen, reacting for two hours, dropwise adding 6.3mmol of tributyltin chloride, heating to-48 ℃, and reacting for 8 hours to generate tin-butylated EDOT (EDOT-SnBu)3)；
2c) Under the protection of nitrogen, adding a certain proportion of Br-EDOT-Br and EDOT-SnBu into a three-neck flask containing a toluene solvent3In the presence of Pd (PPh) as catalyst3)4Carrying out condensation reflux reaction for 12h at 110 ℃ under catalysis; after the reaction is finished, washing the product with water, extracting with chloroform, drying a small amount of anhydrous magnesium sulfate for 24 hours, then distilling under reduced pressure to remove the solvent, purifying and separating with a silica gel chromatographic column, and purifying to obtain a light yellow solid product TriEDOT;
2d) evenly dissolving TriEDOT 4.76mmol in THF, cooling to-78 deg.C, dropwise adding n-BuLi 28.57mmol under nitrogen atmosphere, reacting for two hours, dropwise adding tributyltin chloride 29.00mmol, heating to-48 deg.C, reacting for 8 hours to obtain tin-butylated EDOT (SnBu)3-TriEDOT-SnBu3)；
(3) Synthesis of stretchable conductive polymers based on EDOT oligomers:
3a) under the protection of nitrogen, adding SnBu into a three-neck flask containing toluene solvent in sequence3-triEDOT-SnBu3，②SnBu3-PDCA-SnBu3And thirdly, Br-EDOT-Br according to the following steps: secondly, the step of: (iii) 1.9:0.1:2, 1.5:0.5:2, 1:1:2, 0.5:1.5:2 or 0.1:1.9:2 in the catalyst Pd (PPh)3)4Condensing and refluxing for 24 hours at 110 ℃ under catalysis; after the reaction is finished, washing the product with water, extracting with dichloromethane, drying a small amount of anhydrous magnesium sulfate for 24 hours, then distilling under reduced pressure to remove the solvent to obtain a black solid, dissolving the solid in chloroform, recrystallizing the obtained polymer in n-hexane, petroleum ether and methanol respectively, filtering, and collecting a filter cake; the resulting polymer was subjected to soxhlet extraction in methanol and acetone, respectively, for 24h to recover the polymer solids, to obtain a stretchable conductive polymer based on EDOT oligomer.
5. The hydrogen bond-crosslinked stretchable conductive polymer according to claim 3, characterized by being prepared by the steps of:
(1) synthesis of the stretchable group SnBu3-BPDCA-SnBu3：
1a) 4.10mmol of 2,2 '-bipyridine 5,5' -dicarboxylic acid was suspended in 20mL of thionyl chloride at room temperature, and several drops of Dimethylformamide (DMF) were added to the above suspension, followed by turning into a clear red solution; the solution was continuously stirred for several hours and then distilled under reduced pressure to remove thionyl chloride; washing the light yellow solid remained in the flask with cold dichloromethane for several times to obtain a product 2,2 '-bipyridyl 5,5' -diformyl chloride BPYDC;
1b) 17.80mmol of generated 2,2 '-bipyridyl 5,5' -diformyl chloride and 44.5mmol of 2-thiopheneethylamine are dissolved in 8mL of triethylamine and CH2Cl2Reacting for 12 hours at room temperature in 60mL of mixed solution to generate BPDCA, and separating and purifying by using a silica gel chromatographic column to obtain a yellow solid;
1c) completely dissolving BPDCA2.16mmol in refined THF, cooling to-78 deg.C, dropwise adding n-BuLi 20.80mmol under nitrogen atmosphere, stirring at low temperature for 2h, dropwise adding tributyltin chloride 22.1mmol for reaction for 8h, distilling under reduced pressure to remove solvent after reaction, purifying and separating with silica gel chromatographic column treated with triethylamine to obtain white solid SnBu3-BPDCA-SnBu3；
(2) Synthesis of compound SnBu3-BisProDOT-Bu2-SnBu3：
2a) Dissolving 6.94mmol of 3, 4-dimethoxythiophene and 8.33mmol of 2, 2-dibutyl-1, 3-propanediol in 50mL of toluene, adding 0.02g of p-toluenesulfonic acid under the protection of nitrogen, heating in an oil bath kettle at 110 ℃, refluxing and stirring for 16 hours until the reaction is complete; extracting the obtained product with dichloromethane, standing, mixing organic phases, washing with saturated saline solution, adding anhydrous magnesium sulfate into the obtained organic phase, drying for 24h, vacuum filtering, rotary evaporating to obtain solid, and purifying with silica gel column to obtain colorless liquid ProDOT-Bu2；
2b) ProDOT-Bu23.73mmol, 7.46mmol of Tetramethylethylenediamine (TMEDA) dissolved in 50mL of THF, after cooling to-78 deg.C, n-BuLi 4.48mmol of hexane solution was added under nitrogen, after stirring for 30 minutes, the solution was then transferred to a solution of ferric acetylacetonate in THF, passed through a cannula under nitrogen and the reaction mixture refluxed overnight; removing volatile matter in vacuum, purifying and separating by silica gel chromatographic column to obtain colorless oily liquid BisProDOT-Bu2；
2c) BisProDOT-Bu21.07mmol of the crude product is uniformly dissolved in THF, after the temperature is reduced to-78 ℃, n-BuLi 4.28mmol is added dropwise under the nitrogen atmosphere, after the reaction is carried out for two hours, tributyltin chloride 4.50mmol is added dropwise, after the temperature is increased to-48 ℃, the reaction is carried out for 8 hours, the solvent is removed by reduced pressure distillation, and a silica gel chromatographic column treated by triethylamine is used for purification and separation to obtain colorless liquid, thus generating SnBu3-BisProDOT-Bu2-SnBu3；
(3) The synthesis is based on ProDOT-Bu2Stretchable conductive polymer of oligomer:
3a) under the protection of nitrogen, adding SnBu into a three-neck flask containing toluene solvent in sequence3-BisProDOT-Bu2-SnBu3，②SnBu3-BPDCA-SnBu3，③Br-ProDOT-Bu2-Br, according to (r): secondly, the step of: (iii) 1.9:0.1:2, 1.5:0.5:2, 1:1:2, 0.5:1.5:2 or 0.1:1.9:2 in the catalyst Pd (PPh)3)4Condensing and refluxing for 24 hours at 110 ℃ under catalysis; after the reaction is finishedWashing the product with water, extracting with dichloromethane, drying a small amount of anhydrous magnesium sulfate for 24h, then distilling under reduced pressure to remove the solvent to obtain a black solid, dissolving the solid in chloroform, recrystallizing the obtained polymer in n-hexane, petroleum ether and methanol respectively, filtering, and collecting a filter cake; soxhlet extracting the obtained polymer in methanol and acetone for 24h, collecting polymer solid to obtain the product based on ProDOT-Bu2A stretchable conductive polymer of an oligomer.
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