3,4-ETHYLENEDIOXYTHIOPHENE (EDOT) POLYMER CAPABLE OF SUPERASSEMBLING WITH CARBON-BASED MATERIALS, AND ITS PREPARATION METHOD

Abstract

The present invention belongs to the technical field of organic supermolecules, and specifically discloses a 3,4-ethylenedioxythiophene (EDOT) polymer capable of supramolecular assembly with carbon-based materials, and a preparation method thereof The polymer of the present invention is a polymer with 3,4-ethylenedioxythiophene-2-acetylene as the main chain and alkoxy as the side chain. The polymer is prepared as follows: subjecting EDOT to bromination, to give 2,5-dibromo-3,4-ethylenedioxythiophene; then reacting 2,5-dibromo-3,4-ethylenedioxythiophene and trimethylsilyl acetylene (TMSA) to give bis(trimethylsilyl)-3,4-ethylenedioxythiophene; removing trimethylsilyl (TMS) protecting groups from the bis(trimethylsilyl)-3,4-ethylenedioxythiophene, and subjecting the obtained compound and 2,5-dibromo-3,4-ethylenedioxythiophene to Sonogashira coupling to give an EDOT polymer. The polymer of the present invention can form a supramolecular assembly system with carbon nanotubes (CMTs), which involves 71-71 adsorption of the main chain and entanglement of the side chain.

Claims

1. A 3,4-ethylenedioxythiophene (EDOT) polymer capable of supramolecular assembly with carbon-based materials, having a general structure shown in the following formula: ##STR00003## wherein, n is a natural number greater than zero.

2. A method for preparing an EDOT polymer according to claim 1, comprising the following specific steps: (1) subjecting EDOT to bromination to give 2,5-dibromo-3,4-ethylenedioxythiophene; (2) reacting the 2,5-dibromo-3,4-ethylenedioxythiophene with trimethylsilyl acetylene (IMSA) to give bis(trimethylsilyl)-3,4-ethylenedioxythiophene, and then removing the trimethylsilyl (TMS) groups from the bis(trimethylsilyl)-3,4-ethylenedioxythiophene to give alkynyl-terminated 3,4-ethylenedioxythiophene; and (3) subjecting the alkynyl-terminated 3,4-ethylenedioxythiophene and 2,5-dibromo-3,4-ethylenedioxythiophene to Sonogashira coupling to produce an EDOT polymer.

3. The preparation method according to claim 2, wherein the Sonogashira coupling is conducted by the following specific steps: under a nitrogen atmosphere, adding 2,5-dibromo-3,4-ethylenedioxythiophene, alkynyl-terminated 3,4-ethylenedioxythiophene, CuI, tetrakis(triphenylphosphine)palladium(0) and triphenylphosphine to a reaction flask, and then adding toluene and triethylamine (TEA); after nitrogen replacement is conducted, subjecting the mixture to reaction at-a high temperature; then subjecting the reaction solution to cooling, extraction, drying and concentration to give a yellow viscous liquid; and then subjecting the yellow viscous liquid to methanolltetrahydrofuran (THF) precipitation to give a yellow solid powder.

4. The preparation method according to claim 3, wherein, the high-temperature reaction is conducted at 65° C. to 75° C.

5. The preparation method according to claim 4, wherein, the high-temperature reaction is conducted at 70° C.

6. The preparation method according to claim 5, wherein, the high-temperature reaction is conducted for 24 h.

7. The preparation method according to claim 2, wherein, the brominating agent used for bromination is bromine water, and the EDOT and bromine water have a molar ratio of 1:(2.0-2.5).)

8. The preparation method according, to claim 3, wherein, the brominating agent used for bromination is bromine water, and the EDOT and bromine water have a molar ratio of 1:(2.0-2.5).

9. The preparation method according to claim 7, wherein, the EDOT and the bromine water have a molar ratio of 1:(2.0-2.5).

10. The preparation method according to claim 8, wherein, the EDOT and the bromine water have a molar ratio of 1:(2.0-2.5).

11. A supramolecular self-assembly system of carbon nanotubes (CNTs) including one or more EDOT polymers according to claim 1.

12. A composite material comprising at least one EDOT polymer according to claim 1.

13. A composite material comprising a supramolocular self-assembly system of CNTs according to claim 11.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0020] FIG. 1 shows the nuclear magnetic resonance (NMR) spectrum r 2,5-dibromo-3,4-ethylenedioxythiophene 2;

[0021] FIG. 2 shows the NMR spectrum for the bis(trimethylsilyl)-3,4-ethylenedioxythiophene;

[0022] FIG. 3 shows the NMR spectrum for the alkynyl-terminated 3,4-ethylenedioxythiophene; and

[0023] FIG. 4 shows the NMR spectrum for an EDOT polymer of the present invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0024] In order to further illustrate the present invention, the present invention will be described in detail below in conjunction with examples and accompanying drawings. The accompanying drawings are provided for further explanation of the present application. The schematic examples of the present application and description thereof are provided to illustrate the present application and do not constitute an undue limitation to the present application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the technical field to which the present application belongs.

EXAMPLE 1

[0025] ##STR00002##

Preparation Process of EDOT Polymer 5

[0026] Intermediates 2 to 4 were synthesized according to the steps reported in Chem. Eur. J. 2011, 17, 1473-1484. The 2,5-dibromo-3,4-ethylenedioxythiophene 2 was a white solid, .sup.1H NMR (500 MHz, Chloroform-d) δ 4.26-4.24 (m, 4H). The bis(trimethylsilyl)-3,4-ethylenedioxythiophene 3 was a white solid, NMR (500 MHz, Chloroform-d) δ 4.24 (m, 4H), 0.25 (s, 18H). The alkynyl-terminated 3,4-ethylenedioxythiophene 4 was a white solid, .sup.1H NMR (500 MHz, Chloroform-d) δ 4.24 (s, 4H), 3.29 (s, 2H).

[0027] Polymer 5: Under a nitrogen atmosphere, 2,5-dibromo-3,4-ethylenedioxythiophene 2 (3.0 g, 10 mmol), alkynyl-terminated 3,4-ethylenedioxythiophene (1.9 g, 10 mmol), CuI (0.19 g, 1 mmol), tetrakis(triphenylphosphine)palladium(0) (0.24 g, 0.2 mmol) and triphenylphosphine (0.13 g, 0.5 mmol) were added to a dry 250 mL three-necked flask, and then 100 mL of dried toluene and 20 mL of TEA were added; after nitrogen replacement was conducted three times, and the mixture reacted at 70° C. for 24 h; the reaction system was cooled to room temperature, then subjected to extraction, dried, and concentrated by rotary evaporation to give a yellow viscous liquid; and the yellow viscous liquid was subjected to methanol/THF precipitation to give 2.6 g of yellow-green solid powder. .sup.1H NMR (500 MHz, Chloroform-d) δ 4.26 (m, 19H), 2.23 (s, 2H), 1.99 (s, 2H).

[0028] The afore-mentioned is merely a preferred example of the present invention. All equivalent changes and modifications made in accordance with the claims of the present invention shall fall within the scope of the present invention.