Sulfonated fluorine-containing poly-arylether (arone) and its preparing method and use

Abstract

The present invention relates to one kind of sulfonated fluorene-containing polyaryl ether (ketone) and its application in preparing proton exchanging film. The sulfonated fluorine-containing polyaryl ether (ketone) may be prepared through polymerization of 9, 9-(4, 4-dihydroxyphenyl) fluorene and chloric or fluorous arone (arene) to form polyaryl ether (ketone); and the subsequent sulfonation with chlorosulfonic acid in the controlled consumption for controlled product sulfonation degree. The sulfonated fluorine-containing polyaryl ether (ketone) may be dissolved in different polar solvents before being cast to form single-component film, or be mixed with other polymer material for preparing composite film, or be mixed with heteropoly acid and other inorganic matter for preparing hetero film; and all these kinds of film have the advantages of low cost, high stability, high water absorption, small equivalent molecular weight, etc. and are expected to find use in fuel cell.

Description

technical field

[0001] The invention relates to a class of sulfonated fluorene-containing polyarylethers (ketones), a preparation method thereof and their application in the preparation of proton exchange membranes. Background technique

[0002] Fuel cells have outstanding advantages such as high energy conversion efficiency, environmental friendliness, and no noise. They are considered to be the preferred energy source in the 21st century, and have broad application prospects in aerospace, military, energy, transportation and other fields. Proton exchange membrane fuel cell (PEMFC) is called the fifth-generation fuel cell. In addition to the advantages of general fuel cells, it also has the advantages of rapid start-up at room temperature, no electrolyte loss, easy discharge of water, long life, specific power and Outstanding features such as higher specific energy. Proton exchange membrane (PEM) is one of the core components of PEMFC, and its performance is directly relat...

Examples

Embodiment 1-1

[0031] Example 1-1 Sulfonation of fluorene-containing polyaryletherketone IIa:

[0032] At room temperature, add 0.25mmol of fluorene-containing polyaryletherketone IIa into a 100mL single-necked flask, add 25mL of dichloromethane, and stir it to fully dissolve it. Measure 0.0665ml (1mmol, 0.117g) of chlorosulfonic acid at a ratio of sulfonic acid molecules of 1:4, add 3mL of dichloromethane to prepare a solution, slowly drop it in, stir and react for 5 hours, and a brown precipitate forms , poured out dichloromethane, washed three times with 5mL of n-hexane each time, added 5mL of DMAc, stirred for 1-2 hours to fully dissolve, added 10mL of 3wt% sodium hydroxide solution, stirred for 6 hours, and then added 100mL of 5wt% HCl solution, reacted for 5 hours, and the reaction product was transferred into a dialysis bag, and was dialyzed with deionized water until the water outside the dialysis bag was neutral, and then evaporated to dryness to obtain the sulfonated fluorene-conta...

Embodiment 1-2

[0033] Embodiment 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10 are containing fluorene polyarylether (ketone) IIb~IIj respectively sulfonation, its sulfonation method and steps are the same as in Example 1-1, the difference is that the raw material ratio (the ratio of fluorene structural units to chlorosulfonic acid molecules in the fluorene-containing polyarylether (ketone) molecule) is different, and the obtained The degree of sulfonation of the product (i.e. X 1 +X 2 value) are different, as shown in Table 1:

[0034] Example

[0035] 2. Membrane preparation

Embodiment 2-1

[0036]Example 2-1 Preparation of single-component membrane by sulfonated fluorene-containing polyaryletherketone Ia:

[0037] Take 1 g of the sulfonated fluorene-containing polyaryletherketone Ia prepared according to Example 1-1, add 20 mL of DMAc, stir for 3 hours to dissolve completely, filter, and concentrate the filtrate at 65 ° C until it is estimated that it will not flow out of the glass plate when it is poured on the glass plate Then pour it on a clean glass plate to form a film, put it into a vacuum oven, and evaporate the solvent in a vacuum at a temperature of 40°C to obtain a dry finished single-component film.

[0038] The prepared film was tested with Fenton's reagent to measure its anti-oxidation property, the method is in 30% H 2 o 2 Add 30ppm of FeSO to the solution 4 , at 25°C, put 1cm 2 For the film samples, record the time when the film begins to break down.

[0039] The prepared membrane was acidified with 1M sulfuric acid at 80° C. for 24 hours, and ...

technical field

[0001] The invention relates to a class of sulfonated fluorene-containing polyarylethers (ketones), a preparation method thereof and their application in the preparation of proton exchange membranes. Background technique

[0002] Fuel cells have outstanding advantages such as high energy conversion efficiency, environmental friendliness, and no noise. They are considered to be the preferred energy source in the 21st century, and have broad application prospects in aerospace, military, energy, transportation and other fields. Proton exchange membrane fuel cell (PEMFC) is called the fifth-generation fuel cell. In addition to the advantages of general fuel cells, it also has the advantages of rapid start-up at room temperature, no electrolyte loss, easy discharge of water, long life, specific power and Outstanding features such as higher specific energy. Proton exchange membrane (PEM) is one of the core components of PEMFC, and its performance is directly relat...

Examples

Embodiment 1-1

[0031] Example 1-1 Sulfonation of fluorene-containing polyaryletherketone IIa:

[0032] At room temperature, add 0.25mmol of fluorene-containing polyaryletherketone IIa into a 100mL single-necked flask, add 25mL of dichloromethane, and stir it to fully dissolve it. Measure 0.0665ml (1mmol, 0.117g) of chlorosulfonic acid at a ratio of sulfonic acid molecules of 1:4, add 3mL of dichloromethane to prepare a solution, slowly drop it in, stir and react for 5 hours, and a brown precipitate forms , poured out dichloromethane, washed three times with 5mL of n-hexane each time, added 5mL of DMAc, stirred for 1-2 hours to fully dissolve, added 10mL of 3wt% sodium hydroxide solution, stirred for 6 hours, and then added 100mL of 5wt% HCl solution, reacted for 5 hours, and the reaction product was transferred into a dialysis bag, and was dialyzed with deionized water until the water outside the dialysis bag was neutral, and then evaporated to dryness to obtain the sulfonated fluorene-conta...

Embodiment 1-2

[0033] Embodiment 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10 are containing fluorene polyarylether (ketone) IIb~IIj respectively sulfonation, its sulfonation method and steps are the same as in Example 1-1, the difference is that the raw material ratio (the ratio of fluorene structural units to chlorosulfonic acid molecules in the fluorene-containing polyarylether (ketone) molecule) is different, and the obtained The degree of sulfonation of the product (i.e. X 1 +X 2 value) are different, as shown in Table 1:

[0034] Example

[0035] 2. Membrane preparation

Embodiment 2-1

[0036]Example 2-1 Preparation of single-component membrane by sulfonated fluorene-containing polyaryletherketone Ia:

[0037] Take 1 g of the sulfonated fluorene-containing polyaryletherketone Ia prepared according to Example 1-1, add 20 mL of DMAc, stir for 3 hours to dissolve completely, filter, and concentrate the filtrate at 65 ° C until it is estimated that it will not flow out of the glass plate when it is poured on the glass plate Then pour it on a clean glass plate to form a film, put it into a vacuum oven, and evaporate the solvent in a vacuum at a temperature of 40°C to obtain a dry finished single-component film.

[0038] The prepared film was tested with Fenton's reagent to measure its anti-oxidation property, the method is in 30% H 2 o 2 Add 30ppm of FeSO to the solution 4 , at 25°C, put 1cm 2 For the film samples, record the time when the film begins to break down.

[0039] The prepared membrane was acidified with 1M sulfuric acid at 80° C. for 24 hours, and ...

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