Segmented copolymer of fully sulfonated polymide and partly sulfonated polybutadiene and preparation method thereof

Abstract

The invention discloses a segmented copolymer of fully sulfonated polymide and partly sulfonated polybutadiene and a preparation method thereof. Sulfonated diamino monomer and naphthalene tetracarboxylic acid dianhydride monomer in a specific proportion are used as the raw materials to be subjected to polycondensation to obtain amino-terminated fully sulfonated polymide, and thionyl chloride is used for modifying carboxyl terminated polybutadiene to prepare chloroacyl terminated polybutadiene; the above two prepolymers react under the anhydrous condition, thus the segmented copolymer of fully sulfonated polymide and polybutadiene can be obtained; and finally acetyl sulfonic ester prepared by concentrated sulphuric acid and acetic anhydride is used for carrying out post sulfonation on the polybutadiene segment, thus preparing the segmented copolymer of the fully sulfonated polymide and partly sulfonated polybutadiene. The segmented copolymer of the invention is dissolved in an organic solvent and is coated with membranes, thus preparing proton exchange membranes applied to fuel cells. The membranes have good proton-conducting properties and mechanical properties. The segmented copolymer has extensive application prospect in the field of the proton exchange membranes applied to fuel cells.

Description

technical field

[0001] The invention relates to a fully sulfonated polyimide and partially sulfonated polybutadiene block copolymer and a preparation method thereof. The prepared copolymer can be used to prepare fuel cell proton exchange membranes, and belongs to the technical field of functional polymer materials . Background technique

[0002] In recent years, due to considerations of energy consumption and environmental protection, fuel cells, as an energy conversion device with high efficiency and low pollution, are being more and more widely used in automobiles and other fields. Proton exchange membranes are key components in fuel cells, the most famous of which is the Nafion membrane produced by DuPont in the late 1960s. It has a crystallizable hydrophobic tetrafluoroethylene main chain and multiple perfluoroethylene ether side chains terminated by sulfonic acid groups [Alternative Polymer Systems for Proton Exchange Membranes (PEMs). Chem. Rev. (2004) 104: 4587-4612...

Examples

Embodiment 1

[0030] (a) Dissolve 3.25g of carboxy-terminated polybutadiene in 30g of toluene, add 3g of thionyl chloride and stir evenly; rise to 60°C for 3 hours under nitrogen protection, then rise to 110°C for 12 hours After the reaction is finished, cool down, and remove the remaining thionyl chloride by distillation under reduced pressure, so as to obtain the toluene solution of polybutadiene with acyl chloride terminal;

[0031] (b) Add 4g 4,4'-diaminodiphenyl ether to a round-bottomed flask placed in an ice bath, and slowly add 20g of concentrated sulfuric acid with a mass concentration of 98%; after the solid is completely dissolved, add 20g of The mass concentration is 50% oleum; the mixed solution was stirred in an ice bath for 2 hours, and then raised to 80° C. to continue the reaction for 10 hours; the reaction solution was cooled and slowly poured into 40 g of ice-water mixture to obtain a large amount of white Precipitation; dissolve the precipitate obtained by filtration in ...

Embodiment 2

[0039] (a) Dissolve 6.5g of carboxy-terminated polybutadiene in 40g of toluene, add 6g of thionyl chloride and stir evenly; rise to 70°C for 2 hours under nitrogen protection, then rise to 100°C for 15 hours After the reaction is finished, cool down, and remove the remaining thionyl chloride by distillation under reduced pressure, so as to obtain the toluene solution of polybutadiene with acyl chloride terminal;

[0040] (b) Add 6g of 4,4'-diaminodiphenyl ether to a round-bottomed flask placed in an ice bath, and slowly add 30g of concentrated sulfuric acid with a mass concentration of 98%; after the solid is completely dissolved, add 30g of it dropwise The mass concentration is 50% oleum; the mixed solution was stirred in an ice bath for 2 hours, and then raised to 90° C. to continue the reaction for 8 hours; the reaction solution was cooled and slowly poured into 60 g of ice-water mixture to obtain a large amount of white Precipitation; dissolve the precipitate obtained by f...

Embodiment 3

[0048] (a) Dissolve 9.75g of carboxyl-terminated polybutadiene in 50g of toluene, add 9g of thionyl chloride and stir evenly; rise to 80°C for 1 hour under nitrogen protection, then rise to 90°C for 18 hours After the reaction is finished, cool down, and remove the remaining thionyl chloride by distillation under reduced pressure, so as to obtain the toluene solution of polybutadiene with acyl chloride terminal;

[0049] (b) Add 8g of 4,4'-diaminodiphenyl ether to a round-bottomed flask placed in an ice bath, and slowly add 40g of concentrated sulfuric acid with a mass concentration of 98%; after the solid is completely dissolved, add 40g of it dropwise The mass concentration is 50% oleum; the mixed solution was stirred in an ice bath for 2 hours, and then raised to 100° C. to continue the reaction for 6 hours; the reaction solution was cooled and slowly poured into 80 g of ice-water mixture to obtain a large amount of white Precipitation; dissolve the precipitate obtained by ...

technical field

[0001] The invention relates to a fully sulfonated polyimide and partially sulfonated polybutadiene block copolymer and a preparation method thereof. The prepared copolymer can be used to prepare fuel cell proton exchange membranes, and belongs to the technical field of functional polymer materials . Background technique

[0002] In recent years, due to considerations of energy consumption and environmental protection, fuel cells, as an energy conversion device with high efficiency and low pollution, are being more and more widely used in automobiles and other fields. Proton exchange membranes are key components in fuel cells, the most famous of which is the Nafion membrane produced by DuPont in the late 1960s. It has a crystallizable hydrophobic tetrafluoroethylene main chain and multiple perfluoroethylene ether side chains terminated by sulfonic acid groups [Alternative Polymer Systems for Proton Exchange Membranes (PEMs). Chem. Rev. (2004) 104: 4587-4612...

Examples

Embodiment 1

[0030] (a) Dissolve 3.25g of carboxy-terminated polybutadiene in 30g of toluene, add 3g of thionyl chloride and stir evenly; rise to 60°C for 3 hours under nitrogen protection, then rise to 110°C for 12 hours After the reaction is finished, cool down, and remove the remaining thionyl chloride by distillation under reduced pressure, so as to obtain the toluene solution of polybutadiene with acyl chloride terminal;

[0031] (b) Add 4g 4,4'-diaminodiphenyl ether to a round-bottomed flask placed in an ice bath, and slowly add 20g of concentrated sulfuric acid with a mass concentration of 98%; after the solid is completely dissolved, add 20g of The mass concentration is 50% oleum; the mixed solution was stirred in an ice bath for 2 hours, and then raised to 80° C. to continue the reaction for 10 hours; the reaction solution was cooled and slowly poured into 40 g of ice-water mixture to obtain a large amount of white Precipitation; dissolve the precipitate obtained by filtration in ...

Embodiment 2

[0039] (a) Dissolve 6.5g of carboxy-terminated polybutadiene in 40g of toluene, add 6g of thionyl chloride and stir evenly; rise to 70°C for 2 hours under nitrogen protection, then rise to 100°C for 15 hours After the reaction is finished, cool down, and remove the remaining thionyl chloride by distillation under reduced pressure, so as to obtain the toluene solution of polybutadiene with acyl chloride terminal;

[0040] (b) Add 6g of 4,4'-diaminodiphenyl ether to a round-bottomed flask placed in an ice bath, and slowly add 30g of concentrated sulfuric acid with a mass concentration of 98%; after the solid is completely dissolved, add 30g of it dropwise The mass concentration is 50% oleum; the mixed solution was stirred in an ice bath for 2 hours, and then raised to 90° C. to continue the reaction for 8 hours; the reaction solution was cooled and slowly poured into 60 g of ice-water mixture to obtain a large amount of white Precipitation; dissolve the precipitate obtained by f...

Embodiment 3

[0048] (a) Dissolve 9.75g of carboxyl-terminated polybutadiene in 50g of toluene, add 9g of thionyl chloride and stir evenly; rise to 80°C for 1 hour under nitrogen protection, then rise to 90°C for 18 hours After the reaction is finished, cool down, and remove the remaining thionyl chloride by distillation under reduced pressure, so as to obtain the toluene solution of polybutadiene with acyl chloride terminal;

[0049] (b) Add 8g of 4,4'-diaminodiphenyl ether to a round-bottomed flask placed in an ice bath, and slowly add 40g of concentrated sulfuric acid with a mass concentration of 98%; after the solid is completely dissolved, add 40g of it dropwise The mass concentration is 50% oleum; the mixed solution was stirred in an ice bath for 2 hours, and then raised to 100° C. to continue the reaction for 6 hours; the reaction solution was cooled and slowly poured into 80 g of ice-water mixture to obtain a large amount of white Precipitation; dissolve the precipitate obtained by ...

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