QUINOID CONJUGATED POLYMER AND PREPARATION METHOD AND APPLICATION THEREOF

Abstract

The invention relates to a quinoid conjugated polymer and a preparation method and application thereof. The quinone conjugated polymer is a novel quinoid polymer connected by C═C double bonds and has good conductivity. The monomer used to prepare the quinoid conjugated polymer contains at least two carbonyl groups. The preparation method is simple and does not require oxidation treatment or doping. The quinoid conjugated polymer can exhibit conductivity without being oxidized or doped, can be prepared quickly and conveniently, and can be applied to optoelectronic devices, thus achieving high application value.

Claims

1. A preparation method of a quinoid conjugated polymer, comprising the following steps: S1: putting a monomer compound and a catalyst in a reaction vessel, and performing an operation of vacuuming and nitrogen filling; S2: adding a solvent with a high boiling point into the reaction vessel in the presence of nitrogen; S3: heating the solution to reflux and fully stirring; and S4: cooling the reaction solution to precipitate a solid; wherein, in step S3, the solution is heated to reflux and fully stirred for 6 hours to 100 hours; in step S4, the solid crude product after the reaction is filtered and dried, is subjected to Soxhlet extraction and purification, and the solid obtained after extraction is then dried, and then sublimated under a pressure of 1×10.sup.−3 Pa at a temperature of 250° C. for 5 hours, and collecting a non-volatile solid, thus obtaining the quinoid conjugated polymer of the following structural formula: ##STR00008## where n=4, 5, 6, 7, 8, 9, 10, 11 or 12; R represents H; X represents N or C connected together to form a six-membered aromatic ring.

2. The preparation method of the quinoid conjugated polymer according to claim 1, wherein the catalyst in step S1 is any one or a mixture of more of a Lawson's reagent, a derivative of Lawson's reagent, tetraphosphorus decasulfide, a mixture of hydrogen sulfide and hydrogen chloride, or other polysulfur-containing compounds.

3. The preparation method of the quinoid conjugated polymer according to claim 1, wherein, the solvent with the high boiling point in step S2 is any one or a mixture of more of trichlorobenzene, trimethylbenzene, DMSO, NMP, DMF, DMAC, DMPU, DMI, and diphenyl ether.

4. A quinoid conjugated polymer prepared by the method according to claim 1.

5. A quinoid conjugated polymer prepared by the method according to claim 2.

6. A quinoid conjugated polymer prepared by the method according to claim 3.

7. The quinoid conjugated polymer according to claim 4, used as a conductive material in optoelectronic devices.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG. 1 is a schematic diagram of the synthesis of the invention.

[0030] FIG. 2 is the current density-voltage curve of cell A and cell B in Example 3 of the invention.

DESCRIPTION OF THE EMBODIMENTS

[0031] The embodiments of the invention are only used for illustrative description, and cannot be understood as a limitation of the invention. For those skilled in the art, it is understandable that some common knowledge and descriptions in the embodiments may be omitted.

Example 1

[0032] The preparation process of the quinoid conjugated polymer in this example is as follows:

##STR00005##

[0033] where X represents S or 0.

[0034] Further, the specific preparation method is as follows:

[0035] Phthalimide (IIa, 1 g, 6.89 mmol), Lawson's reagent (2.79 g, 6.89 mmol) and a magnetic stirrer were placed in a 500 ml two-necked flask and a condenser is installed; the flask was subjected to the operation of vacuuming and nitrogen filling through a double-row tube, and this operation was carried out three times; trichlorobenzene (200 ml) was added into the flask in the presence of nitrogen; the solution was heated to reflux and stirred for 72 hours; the reaction solution was cooled to precipitate a solid; the solid was collected by suction filtration and then washed with 30 ml of acetone three times; the solid obtained by suction filtration was dried in a vacuum oven at 100° C. for 10 hours; the solid was finely ground with an agate mortar and then extracted with a Soxhlet extractor for 48 hours; the solid in an extraction sleeve was collected and dried, and the solvent for the extraction was toluene. The dried solid was ground into powder and sublimated in a vacuum sublimation instrument for 5 hours under a pressure of 1×10.sup.−3 Pa at a temperature of 250° C. In the experiment, the non-volatile solid in the sublimation instrument was collected, and its final weight was 0.91 g (the yield is 91%). Solid-state Maldi-Tof mass chromatography: the measured value was 837.00; the calculated value was 837.94 (n=7, X=0). Solid-state nuclear magnetism: .sup.1H NMR (400 MHz) δ [ppm]=7.5, 14. .sup.13C NMR (100 MHz) δ [ppm]=131.

Example 2

[0036] The preparation process of the quinoid conjugated polymer in this example is as follows:

##STR00006##

[0037] where X represents S or 0.

[0038] Further, the specific preparation method is as follows:

[0039] Pyridine 2,3-diimide (IIb, 1 g, 6.75 mmol), a derivative of Lawson reagent (2.73 g, 6.75 mmol) and a magnetic stirrer were placed in a 500 ml two-necked flask and a condenser is installed; the flask was subjected to the operation of vacuuming and nitrogen filling through a double-row tube, and this operation was carried out three times; trimethylbenzene (200 ml) was added into the flask in the presence of nitrogen; the solution was heated to reflux and stirred for 72 hours; the reaction solution was cooled to precipitate a solid; the solid was collected by suction filtration and then washed with 30 ml of acetone three times; the solid obtained by suction filtration was dried in a vacuum oven at 100° C. for 10 hours; the solid was finely ground with an agate mortar and then extracted with a Soxhlet extractor for 48 hours; the solid in an extraction sleeve was collected and dried, and the solvent for the extraction was toluene. The dried solid was ground into powder and sublimated in a vacuum sublimation instrument for 5 hours under a pressure of 1×10.sup.−3 Pa at a temperature of 250° C. In the experiment, the non-volatile solid in the sublimation instrument was collected, and its final weight was 0.85 g (the yield is 85%). Solid-state Maldi-Tof mass chromatography: the measured values were 727.07, 842.09, 958.11; the calculated values were 728.74 (n=6, X=0), 844.85 (n=7, X=0), 766.78 (n=6, X=S), 960.98 (n=8, X=0).

Example 3

[0040] The preparation process of the quinoid conjugated polymer in this example is as follows:

##STR00007##

[0041] where X represents S or 0.

[0042] Further, the specific preparation method is as follows:

[0043] O-pyrazine diimide (IIc, 1 g, 6.71 mmol), phosphorus decasulfide (2.71 g, 6.71 mmol) and a magnetic stirrer were placed in a 500 ml two-necked flask and a condenser is installed; the flask was subjected to the operation of vacuuming and nitrogen filling through a double-row tube, and this operation was carried out three times; diphenyl ether (200 ml) was added into the flask in the presence of nitrogen; the solution was heated to reflux and stirred for 72 hours; the reaction solution was cooled to precipitate a solid; the solid was collected by suction filtration and then washed with 30 ml of acetone three times; the solid obtained by suction filtration was dried in a vacuum oven at 100° C. for 10 hours; the solid was finely ground with an agate mortar and then extracted with a Soxhlet extractor for 48 hours; the solid in an extraction sleeve was collected and dried, and the solvent for the extraction was toluene. The dried solid was ground into powder and sublimated in a vacuum sublimation instrument for 5 hours under a pressure of 1×10.sup.−3 Pa at a temperature of 250° C. In the experiment, the non-volatile solid in the sublimation instrument was collected, and its final weight was 0.93 g (the yield is 93%). Solid-state Maldi-Tof mass chromatography: the measured values were 532.32, 649.26, 765.31, 882.35, 999.35, 1116.36, 1232.39, 1349.42; the calculated values were 532.07 (n=4, X=S), 649.68 (n=5, X=S), 766.78 (n=6, X=S), 883.89 (n=7, X=S), 1001.00 (n=8, X=S), 1118.11 (n=9, X=S), 1235.23 (n=10, X=S), 1352.34 (n=11, X=S), 1469.45 (n=12, X=S). Solid-state nuclear magnetism: .sup.1HNMR (400 MHz) δ [ppm]=9.4. .sup.13C NMR (100 MHz) δ [ppm]=143,119.

TABLE-US-00001 TABLE 1 Conductivity results of the polymers prepared in Examples 1 to 3 Conjugated Conduct- Conduct- Conduct- Conduct- Average polymer ivity ivity ivity ivity S/cm 1a 4.367 4.566 4.785 4.505 4.0 3.484 4.651 3.623 2.347 1b 3.247 3.401 5.291 5.208 4.1 3.497 3.484 3.203 5.263 1c 4.926 5.348 3.906 4.032 4.1 2.653 2.710 5.464 4.082

[0044] The above results are the corresponding conductivity of the polymer products prepared in Examples 1 to 3, sampled for multiple times by powder compression, and tested with a four-probe conductivity tester. It can be seen from the final average value of the conductivity that the conductivity of a quinoid conjugated polymer prepared by the invention is 4.0 S/cm and above on average. It is believed that the quinoid conjugated polymer provided in the invention can be used as an organic conductive material in optoelectronic devices.

[0045] Heterojunction organic solar cells were prepared by mixing polymer PBDB-T and ITIC, in which transparent electrodes were mixtures with PEDOT:PSS and PEDOT:PSS and the product of Example 3 being 10:1, and the metal electrodes were silver, thus obtaining cell A and cell B. The specific results are as follows:

TABLE-US-00002 Voc [V] Jsc [mA cm.sup.−2] FF PCE [%] Cell A 0.88 13.87 62.39 7.61 ± 0.30 Cell B 0.89 13.62 68.42 8.40 ± 0.25

[0046] Obviously, cell B has a significant improvement in cell efficiency due to the effect of Example 3.

[0047] It should be noted that the compound of the invention has poor solubility and cannot be formed into a film, resulting in low conductivity, but its conductivity is greatly improved in solvents or when the compound is dispersed; and because of the low solubility of these compounds, they are conductors in acidic solvents and cannot be subjected to nuclear magnetism measurement, so two of the examples measured solid-state nuclear magnetism.

[0048] It should be noted that the above-described embodiments are examples merely illustrative of the technical solutions of the invention and are not intended to limit the specific embodiments of the invention. Any modification, equivalent replacement and improvement made within the spirit and principle of the claims of the invention shall be included in the protection scope of the claims of the invention.