CN111072959B - Polypyrrole derivative and preparation method and application thereof - Google Patents
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Abstract
The invention relates to a polypyrrole derivative and a preparation method and application thereof. It has the following structural general formula: wherein, -R' is-H or a substituent, -L is selected from-CH 2 ‑、‑C 6 H 5 ‑、‑C 6 H 10 ‑、‑CH＝、＝C＝、‑
COO‑、‑COOR、‑CH 2 CH 2 ‑、‑CH 2 CH 2 CH 2 One or more of-RCONH and-RCONR' -S is selected from-COOH, -COOR, -OH and-SO 3 H、‑NH 2 、‑N + R 3 One or more of imidazolyl and pyridyl, wherein n represents polymerization degree and has a value range of 50-100000 and a molecular weight range of 1 multiplied by 10 3 ～1×10 8 . It has high photothermal conversion efficiency, high water solubility, high photothermal stability and low toxicity, and may be used as photothermal treating agent widely for treating tumor cell. The preparation method is a traditional method. The process is simple and the used equipment is few. The use of the present invention provides a medicament or pharmaceutical composition having potential in the treatment of neoplastic disease using photothermal therapy.
Description
Technical Field
The invention relates to a polypyrrole derivative and a preparation method and application thereof.
Background
Cancer has become a major lethal factor in the world over heart disease. Photothermal therapy is a minimally invasive tumor treatment technology developed in recent years, and the treatment process is as follows: 1) Searching a photothermal therapeutic agent with higher photothermal conversion efficiency, and gathering near tumor tissues through a targeting identification technology and an injection way; 2) Under the irradiation of near infrared light (the wavelength is 700-1100 nm), normal tissues can be prevented from being damaged due to low absorption rate of the near infrared light, and tumor cells can absorb light and heat and are killed. The photothermal therapy has the advantages of being capable of accurately removing tumor cells, having extremely low damage to normal tissues, being controllable in time and space, simple in operation method, few in patient complications, short in hospitalization time and the like, and is expected to be developed into an ideal tumor treatment method for replacing the traditional cancer treatment means.
Photothermal agents are important factors that limit the clinical application of photothermal therapy. Currently, there are two types of photothermal therapeutic agents widely studied, inorganic and organic. Among them, inorganic photothermal therapeutic agents have high photothermal conversion efficiency, but have the disadvantages of difficult degradation, unknown long-term toxicity, high cost, complicated preparation process, poor photothermal stability, and the like, so that clinical application is difficult to realize. The organic photothermal therapeutic agent has good biocompatibility and degradability, but has the defects of poor water solubility, low photothermal conversion efficiency, low photothermal stability and the like. In order to be beneficial to the practical clinical application and effectively avoid unknown long-term toxicity, the development of a novel photothermal therapeutic agent with good water solubility, high photothermal conversion efficiency, photothermal stability and low systemic toxicity has important research significance.
Disclosure of Invention
The invention aims to provide a polypyrrole derivative which has good photothermal conversion efficiency, water solubility and photothermal stability, can be matched with near-infrared laser to act, and can inhibit or kill tumor cells.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a polypyrrole derivative, having the structure of formula (i):
in formula (I), R and R' are-H or a substituent, L is selected from-CH 2 -、-C 6 H 5 -、-C 6 H 10 -、-CH＝、＝C＝、-COO-、-COOR、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 One or more of-RCONH-, -RCONR' -and-S is selected from-COOH, -COOR, -OH and-SO 3 H、-NH 2 、-N + R 3 One or more of imidazolyl and pyridyl, n represents polymerization degree and has the value range of 50-100000 and the molecular weight range of 1 x 10 3 ～1×10 8 。
Another object of the present invention is to provide a method for preparing the polypyrrole derivative, which comprises the following steps:
(1) Carrying out hydrolysis, addition, condensation and cyclization reactions on a compound A with a structure of a formula (II) and a compound B with a structure of a formula (III) in a weak acid and weak base solution environment to obtain a pyrrole derivative monomer;
(2) The pyrrole derivative monomer is subjected to polymerization reaction under the action of an initiator to generate a polypyrrole derivative;
in formula (II), R and R' are-H or a substituent; in the formula (III), -R ", -R'" is-H or a substituent group, -L is selected from-CH 2 -、-C 6 H 5 -、-C 6 H 10 -、-CH＝、＝C＝、-COO-、-COOR、-CH 2 CH 2 -、-CH 2 CH 2 CH 2 One or more of-RCONH and-RCONR' -S is selected from-COOH, -COOR, -OH and-SO 3 H、-NH 2 、-N + R 3 One or more of imidazolyl and pyridyl.
In the preparation method of the polypyrrole derivative of the invention:
in the step (1), the compound A and the compound B are stirred and react for 2 to 90 hours under reflux, then the reaction is finished, and an impurity separation step and a drying step are carried out to obtain a pyrrole derivative monomer; the reaction ratio of the compound A to the compound B is (1-2): (2-1).
Preferably, the weak acid in step (1) is a carboxylic acid, and the weak base is a pyridyl-containing basic organic substance, an imidazolyl-containing basic organic substance, or a carboxylate.
Preferably, the specific steps of step (2) are as follows: respectively dispersing pyrrole derivative monomers and an initiator in a solvent, dripping a dispersion solution containing the initiator into the dispersion solution containing the pyrrole derivative monomers, and stirring and reacting for 12-48 h at normal temperature; then finishing the reaction, and then performing an impurity separation step and a drying step to obtain a polypyrrole derivative; the reaction ratio of the pyrrole derivative monomer to the initiator is (1-2): (1.5-7).
Preferably, the initiator is Fe 3+ Salts and/or ammonium peroxodisulfate.
Preferably, the compound A and the compound B react in a solvent, wherein the solvent is one or more of water, methanol, ethanol, isopropanol, acetone and butanone; the pyrrole derivative monomer and the initiator react in a solvent, wherein the solvent is one or more of water, methanol, ethanol, isopropanol, acetone and butanone.
It is still another object of the present invention to provide a pharmaceutical or pharmaceutical composition comprising said polypyrrole derivative or a polypyrrole derivative prepared by a method for preparing said polypyrrole derivative.
Preferably, the medicament or the pharmaceutical composition further comprises a pharmaceutically acceptable salt.
Preferably, the pharmaceutical agent or pharmaceutical composition is in the form of a solid, liquid or semi-liquid.
The invention has the beneficial effects that:
the polypyrrole derivative provided by the invention is in a powder form, can stably exist in an aqueous solution under the condition of light, can be discharged out of a body through catabolism in the body, and is safe and stable. In addition, the product has obvious photothermal conversion effect, and when near-infrared laser is applied to irradiate the tumor cells wrapped by the polypyrrole derivative solution, the result shows that the product has obvious killing effect on the tumor cells.
The preparation method of the polypyrrole derivative is a traditional method, and has the advantages of simple process and less used equipment.
The use of the present invention provides a medicament or pharmaceutical composition having potential in the treatment of neoplastic disease using photothermal therapy.
Drawings
FIG. 1 is a graph showing the relationship between the irradiation time and temperature of a polypyrrole derivative under 808nm laser irradiation;
FIG. 2 is a graph of the relationship between photothermal agents and cell viability at different concentrations.
Detailed Description
The invention is further illustrated by the following examples 1 to 7.
Example 1:
(1) Weighing 1.41g of 2-aminoethanesulfonic acid, 1.70g of 2, 5-dimethoxy tetrahydrofuran, 14.90g of pyridine, 11.31g of glacial acetic acid and 6.0g of distilled water, putting all the raw materials into a flask, starting stirring, reacting for 56 hours under reflux, concentrating a reaction product through reduced pressure distillation, adding a proper amount of acetone to separate out a solid, filtering, and drying the obtained filter residue in vacuum at 60 ℃ to obtain a pyrrole derivative monomer with the chemical name of 2- (pyrrole-1) ylethanesulfonic acid;
(2) Weighing 1.60g of 2- (pyrrole-1) ethanesulfonic acid and FeCl 3 ·6H 2 Dissolving O7.10 g in 50mL and 100mL of methanol, respectively, to dissolve FeCl 3 ·6H 2 Slowly dropwise adding a methanol solution of O into a methanol solution dissolved with 2- (pyrrole-1) ethanesulfonic acid, transferring the mixed solution into a flask, stirring, reacting at normal temperature for 20 hours, removing the solvent in the reaction product by reduced pressure distillation, adding 100mL of ethanol, stirring, mixing uniformly, standing, filtering, dissolving the obtained filter cake with distilled water, filtering again, removing water from the obtained filtrate by reduced pressure distillation, and drying in vacuum at 60 ℃ to obtain the poly [2- (pyrrole-1) ethanesulfonic acid]。
Example 2:
(1) Adding 4.17g of chloroethyl ammonium chloride into a flask, then slowly dripping 40mL of trimethylamine ethanol solution with the concentration of 33wt%, starting stirring, reacting for 14 hours under reflux, then concentrating by reduced pressure distillation, and then carrying out vacuum drying on a distillation product to obtain trimethylamino ethylammonium chloride;
(2) Putting the dried product, 4.76g of 2, 5-dimethoxytetrahydrofuran, 23.80g of pyridine, 18.07g of glacial acetic acid and 9.7g of distilled water into a flask, starting stirring, and reacting for 72 hours under reflux; carrying out reduced pressure distillation treatment on the reaction product, then adding a proper amount of acetone to separate out solids, then filtering, and drying the obtained filter residue in vacuum at 60 ℃ to obtain a pyrrole derivative monomer with the chemical name of N-trimethyl aminoethyl pyrrole chloride;
(3) Weighing 1.90g of N-trimethylaminoethyl pyrrole chloride and FeCl 3 ·6H 2 Dissolving O6.70 g in 50mL and 100mL of methanol respectively to dissolve FeCl 3 ·6H 2 Slowly dropwise adding the methanol solution of O into the methanol solution dissolved with the N-trimethylammoniumpropyrrole chloride, transferring the mixed solution into a flask, starting stirring, reacting for 24 hours at normal temperature, removing the solvent in the reaction product by reduced pressure distillation, adding a proper amount of ethanol, stirring and mixing uniformly in sequence, standing, filtering, dissolving the obtained filter cake with distilled water, filtering again, removing water from the obtained filtrate by reduced pressure distillation, and drying in vacuum at 60 ℃ to obtain the poly [ N-trimethylammoniumpropyrrole chloride ℃]。
Example 3:
(1) Weighing 4.07g of sodium acetate trihydrate, 1.17g of ethanolamine, 27.59g of glacial acetic acid and 2.3837g of 2, 5-dimethoxy tetrahydrofuran, weighing 12mL of distilled water, putting all the raw materials into a flask, carrying out reflux reaction for 14 hours under the condition of 100 ℃ oil bath, then cooling to the normal temperature, pouring a reaction product into a separating funnel, washing the flask with 30mL of dichloromethane, pouring the washing product into the separating funnel, extracting with 3 mL of 20mL of dichloromethane after liquid separation, collecting an organic phase, neutralizing the pH value of an aqueous phase solution to 7 with saturated sodium bicarbonate, extracting an aqueous phase with 3 mL of 20mL of dichloromethane, combining the two collected organic phases, adding a proper amount of anhydrous sodium sulfate, drying for 8 hours at room temperature, filtering, and removing dichloromethane from the obtained filtrate by using a rotary evaporator to obtain N-hydroxyethyl pyrrole;
(2) Under the ice-bath cooling condition, 6mL of thionyl chloride is dropwise added into 1.716g of N-hydroxyethyl pyrrole, then the mixture reacts for 4 hours at 85 ℃ under the reflux condition, excessive thionyl chloride is removed through distillation, 3X 15mL of methanol is added under stirring, then methanol and HCl are removed through distillation, and N-chloroethyl pyrrole is obtained;
(3) Putting the N-chloroethyl pyrrole into a flask, adding 40mL of ethanol and 0.458g of KI, slowly dropping 15mL of trimethylamine ethanol solution with the concentration of 33wt%, starting stirring, reacting for 8 hours at room temperature, transferring to an oil bath at 80 ℃ for reflux reaction for 6 hours, removing the solvent by distillation, adding 60mL of distilled water, stirring for 8 hours, filtering, adding 100mL of acetone into the obtained filtrate after reduced pressure distillation treatment to separate out a solid, filtering again, and drying the obtained filter residue in vacuum at 60 ℃ to obtain a pyrrole derivative monomer with the chemical name of N-chloroethyl pyrrole chloride;
(4) Weighing 1.88g of the monomer and FeCl 3 ·6H 2 6.69g of O was dissolved in 30mL and 50mL of methanol, respectively, to dissolve FeCl 3 ·6H 2 Slowly dripping the methanol solution of O into the methanol solution dissolved with the pyrrole derivative monomer, stirring and reacting for 24 hours at normal temperature, and removing the solvent by reduced pressure distillation. Adding ethanol, stirring, standing, filtering, dissolving the filter cake with distilled water, filtering, distilling the filtrate under reduced pressure to remove water, and vacuum drying at 60 deg.C to obtain poly [ N-trimethylammonioethylpyrrole chloride]。
In the above-mentioned technical scheme, N-chloroethylpyrrole is commercially available, so that the steps (1) and (2) can be omitted.
Example 4:
(1) Adding 7.90g of ethylammonium bromide and 0.88g of KI into a flask, starting stirring, slowly dripping 40mL of a trimethylamine ethanol solution with the concentration of 33wt%, reacting for 7 hours at room temperature, transferring to an oil bath at 72 ℃, performing reflux reaction for 15.5 hours, removing the solvent by distillation, and performing vacuum drying at 60 ℃ to obtain N-trimethylammoniumpropyrrole bromide;
(2) Adding the N-trimethylaminoethyl pyrrole bromide into a flask, adding 10mL of distilled water, 24.65g of pyridine, 18.74g of glacial acetic acid and 4.94g of 2, 5-dimethoxytetrahydrofuran, carrying out reflux reaction for 60 hours under the condition of an oil bath at 100 ℃, then removing the solvent by distillation, adding 50mL of acetone into the distillation product, stirring for 8 hours, then filtering, and carrying out vacuum drying on filter residues at 60 ℃ to obtain a pyrrole derivative monomer with the chemical name of N-trimethylaminoethyl pyrrole bromide;
(3) Adding 1.79g of 2-N-trimethylethylpyrrole bromide and 20mL of methanol into a flask, slightly shaking to disperse solids, then weighing 4.51g of ferric chloride hexahydrate to dissolve in 20mL of methanol, dripping the obtained methanol solution containing the ferric chloride hexahydrate into the flask, reacting at room temperature for 24 hours, then removing the solvent through reduced pressure distillation, adding 50mL of absolute ethanol into the distillation product, stirring for 10 hours, then filtering, adding 100mL of distilled water into filter residues, stirring for 10 hours, filtering again, removing the solvent from the obtained filtrate through reduced pressure distillation, adding 20mL of absolute ethanol into the distillation product, continuing reduced pressure distillation until the product is nearly dry, and drying in vacuum at 60 ℃ to obtain poly [ N-trimethylethylpyrrole bromide ].
Example 5:
(1) Weighing 4.10g of sodium acetate trihydrate, 3.79g of diethyl aminomalonate hydrochloride, 27.61g of glacial acetic acid and 2.39g of 2, 5-dimethoxytetrahydrofuran, weighing 12mL of distilled water, putting all the raw materials into a flask, carrying out reflux reaction for 14 hours under the condition of 100 ℃ of oil bath, then cooling to the normal temperature, pouring the reaction product into a separating funnel, washing the flask with 30mL of dichloromethane, pouring the washed product into the separating funnel, carrying out extraction by using 3 mL of dichloromethane of 20mL after separating liquid, collecting an organic phase, then neutralizing the pH of an aqueous phase solution to 7 by using saturated sodium bicarbonate, and then extracting an aqueous phase by using 3 mL of 20mL of dichloromethane, combining the organic phases collected twice, adding a proper amount of anhydrous sodium sulfate, drying at room temperature for 8 hours, filtering, removing dichloromethane from the obtained filtrate by using a rotary evaporator, weighing 2.9g of NaOH, weighing 15mL of water to prepare NaOH solution, adding the obtained NaOH solution into the evaporation product under the ice bath condition, gradually heating, reacting under reflux for 4 hours, cooling to room temperature again, neutralizing the reaction product by using concentrated hydrochloric acid until the pH value is 2-3, cooling the product to room temperature by using ice bath, filtering again, and drying filter residues in vacuum to obtain a pyrrole derivative monomer with the chemical name of 2- (pyrrole-1) malonic acid;
(2) Weighing 1.78g of 2- (pyrrole-1) malonic acid and FeCl 3 ·6H 2 Dissolving O7.25 g in methanol 30mL and 50mL respectively, and dissolving FeCl 3 ·6H 2 Slowly dropwise adding a methanol solution of O into a methanol solution dissolved with 2- (pyrrole-1) malonic acid, transferring the mixed solution into a flask, starting stirring, reacting at normal temperature for 24 hours, removing the solvent by reduced pressure distillation, adding a proper amount of ethanol, sequentially stirring, standing, filtering, dissolving the filter cake with distilled water, filtering again, removing water from the obtained filtrate by reduced pressure distillation, and drying in vacuum at 60 ℃ to obtain the poly [2- (pyrrole-1) malonic acid]。
Example 6:
(1) Weighing 4.10g of sodium acetate trihydrate, 3.26g of 3-amino-1, 2-propylene glycol, 55.61g of glacial acetic acid and 4.79g of 2, 5-dimethoxy tetrahydrofuran, weighing 18mL of distilled water, putting all the raw materials into a flask, carrying out reflux reaction for 1 hour under the condition of an oil bath at 100 ℃, then cooling to normal temperature, pouring a reaction product into a separating funnel, washing the flask with 60mL of dichloromethane, pouring the washing product into the separating funnel, extracting with 3X 40mL of dichloromethane after liquid separation, collecting an organic phase, adding a proper amount of anhydrous sodium sulfate, drying for 8 hours at room temperature, filtering, removing dichloromethane from the obtained filtrate by using a rotary evaporator, and carrying out vacuum drying to obtain a pyrrole derivative monomer, wherein the chemical name of the pyrrole derivative monomer is 3- (pyrrole-1) group-1, 2-propylene glycol;
(2) Weighing 2.52g of 3- (pyrrole-1) group-1, 2-propylene glycol and FeCl 3 ·6H 2 O12.25 g was dissolved in 40mL and 80mL of methanol, respectively, and FeCl was dissolved 3 ·6H 2 Slowly dropwise adding methanol solution of O into methanol solution dissolved with 3- (pyrrole-1) yl-1, 2-propylene glycol, stirring at room temperature for 24 hr, distilling under reduced pressure to remove solvent, adding appropriate amount of ethanol, neutralizing with saturated sodium carbonate to pH7Stirring, standing, filtering, soaking filter cake in ethanol, filtering, mixing filtrates, distilling under reduced pressure, and vacuum drying at 60 deg.C to obtain poly [3- (pyrrole-1) yl-1, 2-propylene glycol]。
Example 7:
(1) Weighing 1.57g of 2-aminopropanesulfonic acid, 1.71g of 2, 5-dimethoxy tetrahydrofuran, 15.10g of pyridine and 11.51g of glacial acetic acid, measuring 7mL of distilled water, putting all the raw materials into a flask, starting stirring, reacting for 60 hours under reflux, concentrating by reduced pressure distillation, adding an appropriate amount of acetone to separate out a solid, filtering, and drying the obtained filter residue in vacuum at 60 ℃ to obtain a pyrrole derivative monomer with a chemical name of 3- (pyrrole-1) ylpropanesulfonic acid;
(2) Weighing as 1.55g of 3- (pyrrole-1) yl propanesulfonic acid and FeCl 3 ·6H 2 Dissolving O7.03 g in 50mL and 100mL of methanol, respectively, to dissolve FeCl 3 ·6H 2 Slowly dropwise adding methanol solution of O into methanol solution dissolved with 3- (pyrrole-1) propyl sulfonic acid, transferring the mixed solution into a flask, reacting at normal temperature for 24 hours, removing the solvent by reduced pressure distillation, adding 100mL ethanol, stirring, standing, filtering, dissolving the filter cake with distilled water, filtering again, removing water from the obtained filtrate by reduced pressure distillation, and vacuum drying at 60 ℃ to obtain poly [3- (pyrrole-1) propyl sulfonic acid]。
Performance test:
1. in vitro photothermal effect investigation of polypyrrole derivatives
Taking the polypyrrole derivative obtained in example 1, adjusting the pH of the solution to be neutral by using sodium bicarbonate solution, and irradiating the solution by using near infrared laser with the wavelength of 808nm, wherein the irradiation intensity is 1.0W/cm 2 The irradiation time was 5 minutes, the irradiation distance was 1cm, and the results of photothermal effect measurement are shown in FIG. 1. As can be seen from fig. 1, the temperature of the material increased significantly over time, indicating that the material had a good photothermal effect.
2. Experiment of killing effect of polypyrrole derivative on tumor cells by combining near-infrared laser irradiation
Six groups of experiments are set, namely a blank control group, a negative control group and experiment groups 1-4, wherein the experiments of each group are implemented on a 96-well cell culture plate, and the experiment process is as follows:
1) Configured as a photo-thermal agent: the polypyrrole derivative obtained in example 1 was adjusted to a neutral pH with a sodium bicarbonate solution, and prepared into photothermal agent solutions having concentrations of 0.06mg/mL,0.15mg/mL,3.00mg/mL, and 6.00mg/mL, respectively.
2) A549 cells in log phase are equivalently inoculated to a 96-well cell culture plate, and the inoculation density is 5.0 x 10 3 /cm 2 Every 6 wells are in one group.
3) 0.06mg/mL of photothermal agent solution was added to test group 1, an equal amount of 0.15mg/mL of photothermal agent solution was added to test group 2, an equal amount of 3.00mg/mL of photothermal agent solution was added to test group 3, an equal amount of 6.00mg/mL of photothermal agent solution was added to test group 4, and equal amounts of deionized water were added to the blank control group and the negative control group.
4) Each fraction was irradiated with 808nm near-infrared laser light at an irradiation distance of 1cm at room temperature for 5 minutes.
5-1) after the end of the light irradiation, the blank control group and the negative control group were each 5% CO at 37 ℃ 2 Incubating for 48 hours under saturated humidity conditions; then culture solution in each hole is discarded and replaced by fresh serum culture solution containing 10 percent of evergreen; then 10. Mu.L of MTT with the concentration of 5mg/mL is added into each well, and the culture is continued for 4 hours; finally, DMSO is used for dissolving, and after the crystals are completely dissolved, the cell survival rate can be measured by an enzyme-labeling instrument.
5-2) after the illumination is finished, adding 10 mu L of MTT with the concentration of 5mg/mL into each hole of the experimental groups 1-4, and continuing culturing for 4 hours; finally, the culture is stopped, DMSO is used for dissolving, and after crystals are completely dissolved, the cell survival rate can be measured by an enzyme-labeling instrument.
The MTT is 3- (4, 5-dimethylthiazole-2) -2, 5-diphenyl tetrazole bromide, and the DMSO is dimethyl sulfoxide.
The results of the tests of the experimental groups 1 to 4 are shown in FIG. 2. As can be seen from FIG. 2, the existence of the polypyrrole derivative solution has a significant reduction effect on the survival rate of tumor cells, the concentration of the polypyrrole derivative solution reaches 3mg/mL, and the polypyrrole derivative solution has a 100% function of killing tumor cells. In contrast, the cell viability of the control group after the end of light irradiation was 93%, 91%, 89%, and 87%, respectively.
Table 1: table of six groups of experimental components
3. In vitro stability testing of solutions of polypyrrole derivatives
The polypyrrole derivative obtained in the example 1 is taken, the pH value of the solution is adjusted to be neutral by using a sodium bicarbonate solution, the solution is dissolved by adding distilled water to prepare solutions with the concentrations of 0.06, 0.15, 3.0 and 6.0mg/mL respectively, and the solutions can still exist stably after being placed at normal temperature for 12 months without generating a turbid phenomenon.
Claims (1)
1. A method for preparing polypyrrole derivatives, which is characterized in that: the method comprises the following steps:
(1) Weighing 1.41g of 2-aminoethanesulfonic acid, 1.70g of 2, 5-dimethoxytetrahydrofuran, 14.90g of pyridine, 11.31g of glacial acetic acid and 6.0g of distilled water, putting all the raw materials into a flask, starting stirring, reacting for 56 hours under reflux, concentrating a reaction product through reduced pressure distillation, adding a proper amount of acetone to separate out a solid, filtering, and drying the obtained filter residue in vacuum at 60 ℃ to obtain a pyrrole derivative monomer with a chemical name of 2- (pyrrole-1) ylethanesulfonic acid;
(2) Weighing 1.60g of 2- (pyrrole-1) ethanesulfonic acid and FeCl 3 ·6H 2 Dissolving O7.10 g in 50mL and 100mL of methanol respectively to dissolve FeCl 3 ·6H 2 Slowly dropwise adding a methanol solution of O into a methanol solution dissolved with 2- (pyrrole-1) ethanesulfonic acid, transferring the mixed solution into a flask, stirring, reacting at normal temperature for 20 hours, removing the solvent in the reaction product by reduced pressure distillation, adding 100mL of ethanol, stirring, mixing uniformly, standing, filtering, dissolving the obtained filter cake with distilled water, filtering again, removing water from the obtained filtrate by reduced pressure distillation, and drying in vacuum at 60 ℃ to obtain the poly [2- (pyrrole-1) ethanesulfonic acid]。
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