CN102746511A - Sulfonated polyimide with hydrolysis resistance, and preparation method and application thereof - Google Patents

Abstract

The invention discloses a hydrolysis-resistant sulfonated polyimide, which is one of sulfonated polyimide homopolymers, sulfonated polyimide block copolymers, and sulfonated polyimide random copolymers. species or two or more. The sulfonated polyimide has good hydrolytic stability, especially the hydrolytic stability at high temperature, and can be used for preparing sulfonated polyimide-based proton exchange membrane materials. The invention also discloses a preparation method of the hydrolysis-resistant sulfonated polyimide and the proton exchange membrane material based on the sulfonated polyimide. The method is simple, easy to operate and control, and is suitable for industrial production.

Description

Hydrolysis-resistant sulfonated polyimide and its preparation method and application

technical field

The invention relates to the field of polymers, in particular to a hydrolysis-resistant sulfonated polyimide and its preparation method and application.

Background technique

With the depletion of coal, oil, natural gas and other energies that can be supplied by nature and the increasing emphasis on environmental protection in countries all over the world, fuel cells, as a clean, efficient and safe green new energy, have shown attractive and broad prospects. market development prospects. As the fifth-generation fuel cell, proton exchange membrane fuel cell (PEMFC) has the advantages of high energy conversion rate, fast start-up at room temperature, no electrolyte leakage, simple structure, and low cost. The fastest type of fuel cell. Proton exchange membrane (PEM) is the core component of proton exchange membrane fuel cell, and its performance directly determines the service life, operation stability and fuel utilization efficiency of the fuel cell.

系列膜和Dow化学公司生产的

膜。这类膜具有优越的机械稳定性、物理化学稳定性以及高的质子传导率。但是，由于它们的成本昂贵、高温下性能大幅下降、甲醇渗透率很高以及带来环境污染等缺点严重限制了其广泛的应用。因此，开发新型高性能且价格低廉的质子交换膜材料是一件非常有意义的工作。磺化芳香族聚合物，由于其优异的热、机械性能和良好的质子传导率作为质子交换膜材料被人们广泛研究，如磺化聚苯(Cy H.Fujimoto et al.，macromolecules，2005，38，5010)、磺化聚醚醚酮(K.D.Kreuer，J.Membr.Sci.，2001，185，29)、磺化聚砜(Z.W.Bai，T.D.Dang，Macromol.RapidCommun.，2006，27，1271)等。其中，磺化聚酰亚胺基质子交换膜(S.Faureet al.，US Pat.6245881；W.Essafi et al.，Macromolecules，2004，37，1431)以其优异的热和机械性能、甲醇阻隔性能和质子传导性引起人们广泛重视。At present, the proton exchange membranes used in PEMFC are almost all perfluorosulfonic acid membranes (PFSA), the most representative of which is produced by Dupont in the United States.

series membranes and manufactured by Dow Chemical Company

membrane. Such membranes have superior mechanical stability, physicochemical stability, and high proton conductivity. However, their disadvantages such as high cost, large performance degradation at high temperature, high methanol permeability, and environmental pollution severely limit their wide application. Therefore, it is a very meaningful work to develop new high-performance and low-cost proton exchange membrane materials. Sulfonated aromatic polymers have been widely studied as proton exchange membrane materials due to their excellent thermal and mechanical properties and good proton conductivity, such as sulfonated polyphenylene (Cy H.Fujimoto et al., macromolecules, 2005, 38 , 5010), sulfonated polyetheretherketone (KDKreuer, J.Membr.Sci., 2001, 185, 29), sulfonated polysulfone (ZWBai, TDDang, Macromol. Rapid Commun., 2006, 27, 1271), etc. Among them, sulfonated polyimide-based proton exchange membranes (S.Faure et al., US Pat.6245881; W.Essafi et al., Macromolecules, 2004, 37, 1431) are known for their excellent thermal and mechanical properties, methanol barrier Performance and proton conductivity have drawn much attention.

However, an important bottleneck limiting the application of polyimide-based proton exchange membranes is the poor hydrolytic stability of the membranes at high temperatures, which cannot meet the application requirements (M.A.Hickner, Chem. Rev. 2004, 4587). At present, 1,4,5,8-naphthalene tetracarboxylic anhydride (NTDA) is mainly used as the material of polyimide-based proton exchange membrane, and people mainly improve the hydrolytic stability of the polymer by synthesizing diamine with strong basicity. However, this method has limited scope for improving hydrolysis resistance and is difficult to synthesize.

Contents of the invention

The invention provides a hydrolysis-resistant sulfonated polyimide.

The invention also provides a preparation method of hydrolysis-resistant sulfonated polyimide, which has simple process and easy operation.

A hydrolysis-resistant sulfonated polyimide, which is a sulfonated polyimide homopolymer composed of structural units represented by formula I, a sulfonated polyimide homopolymer composed of structural units represented by formula I and structural units represented by formula II One or more of imide block copolymers, sulfonated polyimide random copolymers composed of structural units shown in formula I and structural units shown in formula II;

The molar percentage of the structural unit represented by formula I in the sulfonated polyimide block copolymer is 2%-98%;

The molar ratio of the structural unit shown in formula I to the structural unit shown in formula II in the sulfonated polyimide random copolymer is greater than or equal to 1:9;

结构中的一种；where _X1 refers to a residue, is

one of the structures

结构中的一种； _X2 refers to a residue that is

one of the structures

_X1 and _X2 can be the same or different;

Ar ₁ is a sulfonated diamine residue; Ar ₂ is a common diamine residue.

The molecular weight of the sulfonated polyimide has no significant impact on its hydrolysis resistance, so the molecular weight of the sulfonated polyimide is not particularly limited; when the sulfonated polyimide is used When preparing the film, in order to facilitate its application, the comparative logarithmic viscosity of the sulfonated polyimide is generally 0.30dL/g-2.00dL/g, which can form a tough film, wherein the viscosity test conditions are: Tested in m-cresol, the temperature is 30°C; the concentration is 0.5g/dL.

In the field of polymers, the content of each structural unit in a polymer can generally be controlled by the feed ratio of raw materials, and the content of each structural unit in the sulfonated polyimide can also be controlled by the feed ratio of raw materials.

The content of each structural unit in the sulfonated polyimide has good hydrolysis resistance within the stated range.

In order to achieve a better inventive effect, preferably:

The sulfonated diamine residue is selected from any one of the following groups:

The common diamine residue is selected from any one of the following groups:

The preparation method of the hydrolysis-resistant sulfonated polyimide includes: the preparation of the sulfonated polyimide homopolymer, the preparation of the sulfonated polyimide block copolymer and/or The preparation of described sulfonated polyimide random copolymer, the obtained sulfonated polyimide homopolymer, sulfonated polyimide block copolymer, sulfonated polyimide random copolymer One or a mixture of two or more of them is used as a hydrolysis-resistant sulfonated polyimide.

The preparation method of described sulfonated polyimide homopolymer comprises the following steps:

Dissolve the sulfonated diamine and tertiary amine in a nitrogen-protected phenolic solvent, then add bis-naphthalene dianhydride and a catalyst; first raise the temperature to 60°C-100°C for 1h-24h, then raise the temperature to 160°C-200°C to continue the reaction 4h-48h, after cooling, pour the solution into the precipitant, collect the precipitate, wash and dry to obtain the sulfonated polyimide homopolymer.

The preparation method of described sulfonated polyimide block copolymer, comprises the following steps:

(a) Dissolve sulfonated diamine and tertiary amine in a nitrogen-protected phenolic solvent, then add bis-naphthalene dianhydride; first raise the temperature to 60°C-100°C for 1h-24h, then raise the temperature to 160°C-200°C to continue React for 4h-48h to obtain a sulfonated polyamic acid oligomer that is terminated by an amino group or an anhydride group and whose main chain contains a sulfonic acid group;

(b) dissolving ordinary diamine and bis-naphthalene dianhydride in a nitrogen-protected phenolic solvent, raising the temperature to 100°C-200°C for 4h-48h to obtain an anhydride group or amino-terminated polyamic acid oligomer;

(c) Mix the sulfonated polyamic acid oligomer in step (a) and the polyamic acid oligomer in step (b), add a catalyst, raise the temperature to 160°C-200°C and continue the reaction for 4h-48h, cool Finally, the solution is poured into a precipitating agent, the precipitate is collected, washed and dried to obtain a sulfonated polyimide block copolymer.

The preparation method of described sulfonated polyimide random copolymer, comprises the following steps:

Dissolve the sulfonated diamine and tertiary amine in a nitrogen-protected phenolic solvent, then add bis-naphthalene dianhydride, common diamine and catalyst, react at 60°C-100°C for 1h-24h, then raise the temperature to 160°C-200°C Continue to react for 4h-48h, pour the solution into the precipitating agent after cooling, collect the precipitate, wash and dry to obtain the sulfonated polyimide random copolymer.

The phenolic solvent can be a phenolic solvent commonly used in this field, such as aromatic phenol, preferably one or more of phenol, m-cresol, mixed cresol, and p-chlorophenol. The mixed cresol is a mixture of three cresol isomers in m-position, p-position and ortho-position, among which m-cresol is the main one, and commercially available products are selected.

The catalyst is preferably one or more of zinc chloride, benzoic acid, isoquinoline, quinoline, triethylenediamine, benzyltrimethylammonium hydroxide, and 1,8-bisdimethylaminonaphthalene .

The amount of the catalyst used is not strictly limited. In order to save resources, the ratio of the amount of the catalyst to the amount of bis-naphthalene dianhydride is preferably 0.2-2.

The tertiary amine is preferably one or more of triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine and pyrrole.

The ratio of the amount of the tertiary amine to the sulfonated diamine is preferably 2-3.

The precipitating agent is preferably one or more of acetone, methanol, ethanol and isopropanol.

The amount of the precipitating agent is not strictly limited. In order to save resources, the volume ratio of the precipitating agent to the phenol solvent is preferably 5-50.

The common diamine mentioned above is a diamine that does not contain sulfonated groups such as sulfonic acid groups. There is no strict limit on the relationship between the amount of sulfonated diamine and common diamine. It can be determined according to the composition of the designed product during actual operation. .

Described sulfonated diamine can select any one in following compound for use:

Described common diamine can select any one in following compound for use:

Described bis-naphthalene dianhydride can be selected any one of the following compounds:

The hydrolysis-resistant sulfonated polyimide can be used to prepare sulfonated polyimide-based proton exchange membrane materials.

The method for the described sulfonated polyimide based proton exchange membrane material is:

Dissolving the hydrolysis-resistant sulfonated polyimide in a solvent to obtain a solution with a solid content of 2%-30% of the polymer, filtering, and then drying the obtained filtrate at 60°C-120°C for 10h-24h after being cast into a film, Then dry at 120°C-180°C for 12h-24h, then immerse the membrane in ethanol and deionized water to wash thoroughly, put it in a sulfuric acid solution with a concentration of 0.5mol/L-4mol/L, and keep it at 20°C-60°C Keep it for 1 day to 7 days, and then wash it with water to obtain a sulfonated polyimide-based proton exchange membrane.

The solvent can be a commonly used organic solvent, such as m-cresol, N-methylpyrrolidone and the like.

The polyimide-based proton exchange membrane material can be applied to proton exchange membrane fuel cell or direct methanol fuel cell diaphragm and related fields.

Compared with the prior art, the present invention has the following beneficial effects:

The sulfonated polyimide of the present invention, due to the basic skeleton structure of bis-naphthalene dianhydride coupled with the electron-donating group, makes the dianhydride have a lower electron nucleophilic potential (E _a ), and the orphan on the electron-donating group The pair of electrons can be delocalized to the imide ring of sulfonated polyimide, which increases the electron cloud density on the imide ring, thereby greatly improving the hydrolytic stability of sulfonated polyimide, especially at high temperature. Hydrolytic stability. At the same time, the sulfonated polyimide-based proton exchange membrane material derived from sulfonated polyimide of the present invention not only has excellent hydrolytic stability and good proton conductivity, but also has good dimensional stability, especially at high temperature. The dimensional stability of the existing polyimide-based proton exchange membrane is not resistant to hydrolysis at high temperature, and the dimensional stability of the high-sulfonated membrane is poor. The sulfonated polyimide-based proton exchange membrane material of the invention has good application prospects in related fields such as proton exchange membrane fuel cells and direct methanol fuel cell electrolyte membranes.

The preparation method of the sulfonated polyimide and the sulfonated polyimide-based proton exchange membrane material of the invention is simple, easy to operate and control, and suitable for industrial production.

Description of drawings

N-324在100％湿度下的电导率随温度变化曲线；Fig. 1 is the sulfonated polyimide matrix proton exchange membrane prepared in embodiment 1 and the U.S. Du pont company's production

The conductivity versus temperature curve of N-324 at 100% humidity;

Fig. 2 is the tensile stress-strain curve of the sulfonated polyimide-based proton exchange membrane prepared in Example 13 after being hydrolyzed in an autoclave at 140°C for 24 hours and before the hydrolysis test.

Detailed ways

The present invention will be further described in detail below in conjunction with specific examples. It must be pointed out that this example is only used to further illustrate the present invention and should not be construed as limiting the protection scope of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the content of the above invention.

Example 1:

Add 10mmol 4,4′-diaminobiphenyl-2,2′-disulfonic acid and 21mmol triethylamine into 56mL m-cresol, and wait for 4,4′-diaminobiphenyl-2,2′-disulfonic acid After the sulfonic acid was completely dissolved, 10 mmol of 4,4'-(4",4'''-dioxy-diphenylsulfone)-1,1',8,8'-naphthalene tetracarboxylic dianhydride and 10 mmol of benzoic acid were added. First raise the temperature to 100°C for 2 hours, then raise the temperature to 200°C for 4 hours. After cooling, pour it into 600mL acetone to obtain a fibrous solid, which is fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.42dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

The infrared spectrum characterization of the obtained polymer: the typical absorption peaks of the imide ring: 1708cm ^-1 (C=O asymmetric stretching vibration), 1668cm ^-1 (C=O symmetric stretching vibration), 1366cm ^-1 (CN stretching vibration vibration); typical absorption peaks of sulfonic acid groups: 1193cm ^-1 (O=S=O asymmetric stretching vibration), 1041cm ^-1 (O=S=O symmetrical stretching vibration).

The polymer obtained is a sulfonated polyimide homopolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the obtained filtrate was cast on a clean glass plate to form a film, then dried at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The exchange membrane has a thickness of 42 μm and a conductivity of 0.11 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane maintains 89% compared with that before hydrolysis.

Example 2:

Add 10mmol 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid and 23mmol triethylamine to 60mL m-cresol, etc. 4,4'-diaminodiphenyl ether-2,2' -After disulfonic acid is completely dissolved, add 10mmol 4,4'-(4",4'''-dimercaptobenzophenone)-1,1',8,8'-naphthalene tetracarboxylic dianhydride and 12mmol triethylene Diamine. First raise the temperature to 100°C for 2 hours, then raise the temperature to 200°C for 6 hours. After cooling, pour it into 800mL acetone to obtain a fibrous solid, which is fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.45dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1708cm ^-1 , 1669cm ^-1 , 1366cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1028cm ^-1 .

The polymer obtained is a sulfonated polyimide homopolymer with the following general structural formula:

The obtained dry polyimide powder was dissolved in N-methylpyrrolidone, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 45 μm and a conductivity of 0.12 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane maintains 82% compared with that before hydrolysis.

Example 3:

Add 10mmol 9,9′-bis(4-aminophenyl)fluorene-2,7′disulfonic acid and 20mmol tri-n-butylamine into 68mL m-cresol, and treat 9,9′-bis(4-aminophenyl) After completely dissolving fluorene-2,7'disulfonic acid, add 10mmol 4,4'-(4",4'''-dioxy-diphenylisohexafluoropropane)-1,1',8 , 8'-naphthalene tetracarboxylic dianhydride and 12mmol triethylenediamine. First heat up to 80°C for 2h, then heat up to 180°C for 16h. After cooling, pour into 800mL ethanol to obtain a fibrous solid, fully wash and Dry to obtain the polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.41dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL)

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1707cm ^-1 , 1666cm ^-1 , 1366cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1022cm ^-1 .

The polymer obtained is a sulfonated polyimide homopolymer with the following general structural formula:

The obtained dry polyimide powder was dissolved in N-methylpyrrolidone, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 36 μm and a conductivity of 0.09 S/cm (70° C., 100% relative humidity); after hydrolysis in a high-pressure reactor at 140° C. for 24 hours, the mechanical strength of the membrane maintains 95% compared with that before hydrolysis.

Example 4:

Add 10mmol 4,4'-diaminodiphenylmethane-2,2'disulfonic acid and 24mmol triethylamine into 50mL m-cresol, and wait for 4,4'-diaminodiphenylmethane-2,2'disulfonic acid After the sulfonic acid is completely dissolved, add 10 mmol 4,4'-(4",4'''-dioxy-diphenylisohexafluoropropane)-1,1',8,8'-naphthalene tetracarboxylic dianhydride And 15mmol of benzoic acid. First heat up to 80°C for 4h, then heat up to 170°C for 24h. After cooling, pour into 500mL acetone to obtain a fibrous solid, fully wash and dry to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.46dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1708cm ^-1 , 1665cm ^-1 , 1367cm ^-1 ; typical absorption peaks of sulfonic acid group: 1191cm ^-1 , 1026cm ^-1 .

The polymer obtained is a sulfonated polyimide homopolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 39 μm and a conductivity of 0.10 S/cm (70° C., 100% relative humidity); after hydrolysis in a high-pressure reactor at 140° C. for 24 hours, the mechanical strength of the membrane maintains 95% compared with that before hydrolysis.

Example 5:

Add 10mmol 4,4'-diamino-4", 4"'diphenoxybiphenyl-3", 3"'disulfonic acid and 24mmol triethylamine to 60mL p-chlorophenol, and wait for 4,4' -Diamino-4", 4'''-diphenoxybiphenyl-3", 3'''-disulfonic acid is completely dissolved, add 10mmol 4,4'-sulfur-1,1',8, 8'-naphthalene tetracarboxylic dianhydride and 15 mmol of triethylenediamine. The temperature was first raised to 80°C for 1 hour, and then the temperature was raised to 190°C for 10 hours. After cooling, pour it into 800mL ethanol to obtain a fibrous solid, which is fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.50dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1708cm ^-1 , 1665cm ^-1 , 1367cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1024cm ^-1 .

The polymer obtained is a sulfonated polyimide homopolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 40 μm and a conductivity of 0.16 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane maintains 91% compared with that before hydrolysis.

Embodiment 6:

First, in a reaction system, 5mmol 4,4'-diaminobiphenyl-2,2'-disulfonic acid and 11mmol triethylamine were added to 30mL m-cresol, such that 4,4'-diaminobiphenyl -2,2'-disulfonic acid is completely dissolved, then add 5.05mmol 4,4'-(4",4"'dioxy-diphenylsulfone)-1,1',8,8'-naphthalene tetra Formic acid dianhydride; raise the temperature of the system to 80°C for 4h, then raise the temperature to 160°C for 10h to obtain a sulfonated polyamic acid oligomer; in another reaction system, add 5mmol m-phenylenediamine, 4.95mmol 4, 4'-(4",4'''-dioxy-diphenylsulfone)-1,1',8,8'-naphthalene tetracarboxylic dianhydride and 30mL m-cresol; then heated to 120°C for 10h, Obtain polyamic acid oligomer; then combine the two reaction systems, add 12mmol benzoic acid at the same time, and then raise the temperature to 190°C for 20h. After cooling, pour it into 800mL acetone to obtain a fibrous solid, fully wash and dry, to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.47dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1708cm ^-1 , 1669cm ^-1 , 1367cm ^-1 ; typical absorption peaks of sulfonic acid group: 1193cm ^-1 , 1040cm ^-1 .

The polymer obtained is a sulfonated polyimide block copolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 44 μm and a conductivity of 0.05 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane maintains 98% compared with that before hydrolysis.

Embodiment 7:

First, in a reaction system, 5mmol 4,4'-diaminodiphenylmethane-2,2'-disulfonic acid and 11mmol triethylamine were added to 32mL m-cresol, such that 4,4'-diaminodiphenylmethane After the complete dissolution of phenylmethane-2,2'-disulfonic acid, add 5.03mmol 4,4'-(4",4'''-dioxy-diphenylsulfone)-1,1',8,8 ′-naphthalene tetracarboxylic dianhydride; the system was heated to 80°C for 2 hours, and then heated to 160°C for 12 hours to obtain a sulfonated polyamic acid oligomer; in another reaction system, 5 mmol 4,4′- Diaminodiphenyl ether, 4.97mmol 4,4'-(4",4'''-dioxy-diphenylsulfone)-1,1',8,8'-naphthalene tetracarboxylic dianhydride and 30mL m-form Phenol, and then heated to 120 ° C for 10 hours to obtain polyamic acid oligomers. Then the two reaction systems were combined, and 13 mmol of benzoic acid and 10 mL of m-cresol were added at the same time, and then the temperature was raised to 195° C. for 10 h. After cooling, pour it into 800mL acetone to obtain a fibrous solid, which is fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.49dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1707cm ^-1 , 1669cm ^-1 , 1364cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1026cm ^-1 .

The polymer obtained is a sulfonated polyimide block copolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 49 μm and a conductivity of 0.04 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane remains 96% compared with that before hydrolysis.

Embodiment 8:

First, in a reaction system, 5mmol 4,4'-diaminobiphenyl-2,2'-disulfonic acid and 11mmol tri-n-butylamine were added to 30mL m-cresol, and 4,4'-diaminobiphenyl After benzene-2,2'-disulfonic acid is completely dissolved, add 4.97mmol 4,4'-(4",4'''-dimercaptobenzophenone)-1,1',8,8'-naphthalene Tetraformic acid dianhydride: raise the temperature of the system to 80°C for 4 hours, then raise the temperature to 180°C for 10 hours to obtain sulfonated polyamic acid oligomers. In another reaction system, add 5 mmol 4,4'-diaminodi Phenyl ether, 5.03mmol 4,4'-(4",4'''-dimercaptobenzophenone)-1,1',8,8'-naphthalene tetracarboxylic dianhydride and 30mL m-cresol, then heated to React at 120°C for 10 hours to obtain a polyamic acid oligomer. Subsequently, the two reaction systems were combined, and 15 mmol of triethylenediamine was added at the same time, and then the temperature was raised to 190° C. for 18 hours. After cooling, pour it into 900mL of ethanol to obtain a fibrous solid, which is fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.75dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1709cm ^-1 , 1669cm ^-1 , 1365cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1028cm ^-1 .

The polymer obtained is a sulfonated polyimide block copolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 36 μm and a conductivity of 0.05 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane remains 91% compared with that before hydrolysis.

Embodiment 9:

First, in a reaction system, 5mmol 9,9'-bis(4-aminophenyl)fluorene-2,7'-disulfonic acid and 13mmol tri-n-butylamine were added to 35mL m-cresol, etc. 9,9 After '-bis(4-aminophenyl)fluorene-2,7'-disulfonic acid is completely dissolved, add 5.01mmol 4,4'-(4",4'''-dimercaptobenzophenone)-1 , 1′,8,8′-naphthalenetetracarboxylic dianhydride, while raising the temperature of the system to 80°C for 3 hours, and then raising the temperature to 180°C for 8 hours to obtain sulfonated polyamic acid oligomers. In another reaction system , add 5mmol 3,4'-diaminodiphenyl ether, 4.99mmol 4,4'-thio-1,1',8,8'-naphthalene tetracarboxylic dianhydride and 20mL m-cresol, then heat up to 100°C for reaction 16h, polyamic acid oligomer was obtained. Then the two reaction systems were combined, and 15mmol benzoic acid was added at the same time, and then the temperature was raised to 190°C for 18h. After cooling, it was poured into 600mL ethanol to obtain a fibrous solid, which was fully washed and dried Dry to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.78dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1707cm ^-1 , 1668cm ^-1 , 1365cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1023cm ^-1 .

The polymer obtained is a sulfonated polyimide block copolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 39 μm and a conductivity of 0.04 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane remains 93% compared with that before hydrolysis.

Example 10:

First, in a reaction system, 5mmol 9,9'-bis(4-aminophenyl)fluorene-2,7'-disulfonic acid and 13mmol tri-n-butylamine were added to 35mL m-cresol, etc. 9,9 After '-bis(4-aminophenyl)fluorene-2,7'-disulfonic acid was completely dissolved, 5.06 mmol of 4,4'-(4",4'''-dioxy-diphenyliso Hexafluoropropane)-1,1',8,8'-naphthalene tetracarboxylic dianhydride, while raising the temperature of the system to 80°C for 4 hours, and then raising the temperature to 170°C for 12 hours to obtain a sulfonated polyamic acid oligomer. In another reaction system, add 5mmol m-phenylenediamine, 4.94mmol 4,4'-sulfur-1,1',8,8'-naphthalene tetracarboxylic dianhydride and 20mL m-cresol, then heat up to 110°C for reaction 16h, polyamic acid oligomer was obtained. Then the two reaction systems were combined, and 15mmol benzoic acid was added at the same time, and then the temperature was raised to 190°C for 18h. After cooling, it was poured into 800mL ethanol to obtain a fibrous solid, which was fully washed and dried Dry to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.51dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1706cm ^-1 , 1668cm ^-1 , 1364cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1023cm ^-1 .

The polymer obtained is a sulfonated polyimide block copolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 50 μm and a conductivity of 0.04 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane remains 98% compared with that before hydrolysis.

Example 11:

First add 7mmol 4,4'-diaminobiphenyl-2,2'-disulfonic acid and 19mmol tri-n-butylamine into 80mL p-chlorophenol, and wait for 4,4'-diaminobiphenyl-2,2' - After the disulfonic acid has completely dissolved; 3 mmol m-phenylenediamine, 10 mmol 4,4'-thio-1,1',8,8'-naphthalenetetracarboxylic dianhydride and 12 mmol benzoic acid are added. The temperature was first raised to 80°C for 2 hours, and then the temperature was raised to 192°C for 10 hours. After cooling, pour it into 2000mL acetone to obtain a fibrous solid, which is fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.61dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1707cm ^-1 , 1668cm ^-1 , 1365cm ^-1 ; typical absorption peaks of sulfonic acid group: 1193cm ^-1 , 1039cm ^-1 .

The polymer obtained is a sulfonated polyimide random copolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the resulting filtrate was cast on a clean glass plate to form a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 45 μm and a conductivity of 0.12 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane remains 88% compared with that before hydrolysis.

Example 12:

First add 5mmol 4,4'-diaminobiphenyl-2,2'-disulfonic acid and 11mmol triethylamine into 80mL m-cresol, and wait for 4,4'-diaminobiphenyl-2,2'- After disulfonic acid is completely dissolved; add 5mmol m-phenylenediamine, 10mmol 4,4'-(4",4"'dioxy-diphenylisohexafluoropropane)-1,1',8,8'- Naphthalene tetracarboxylic dianhydride and 12 mmol triethylenediamine. The temperature was first raised to 80°C for 2 hours, and then the temperature was raised to 192°C for 10 hours. After cooling, pour it into 1000mL ethanol to obtain a fibrous solid, which is fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.48dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1707cm ^-1 , 1668cm ^-1 , 1365cm ^-1 ; typical absorption peaks of sulfonic acid group: 1193cm ^-1 , 1040cm ^-1 .

The polymer obtained is a sulfonated polyimide random copolymer with the following general structural formula:

The obtained dried polyimide powder was dissolved in m-cresol, and the solid content of the polymer was 10 wt.%. After the polymer is completely dissolved, filter, pour the filtrate on a clean glass plate, dry at 80°C for 10h, and then dry at 120°C for 12h. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 45 μm and a conductivity of 0.05 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane maintains 95% compared with that before hydrolysis.

Example 13:

First add 9mmol 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid and 19.8mmol triethylamine into 60mL m-cresol, etc. 4,4'-diaminodiphenyl ether-2, After 2′-disulfonic acid is completely dissolved; add 1mmol 4,4′-diaminodiphenyl ether, 10mmol 4,4′-(4″,4″′dimercaptobenzophenone)-1,1′,8, 8'-naphthalene tetracarboxylic dianhydride and 10 mmol of triethylenediamine. The temperature was first raised to 100°C for 2 hours, and then the temperature was raised to 200°C for 24 hours. After cooling, pour it into 900mL acetone to obtain a fibrous solid, which is fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.56dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1708cm ^-1 , 1669cm ^-1 , 1366cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1028cm ^-1 .

The polymer obtained is a sulfonated polyimide random copolymer with the following general structural formula:

The obtained dry polyimide powder was dissolved in N-methylpyrrolidone, and the solid content of the polymer was 10 wt.%. After the polymer is completely dissolved, filter, pour the filtrate on a clean glass plate, dry at 80°C for 10h, and then dry at 120°C for 12h. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 45 μm and a conductivity of 0.11 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane maintains 90% compared with that before hydrolysis.

Example 14:

First add 4mmol 4,4'-diaminodiphenyl ether-2,2'-disulfonic acid and 9mmol triethylamine into 60mL m-cresol, etc. 4,4'-diaminodiphenyl ether-2,2 After the ′-disulfonic acid is completely dissolved; add 6mmol 9,9′-bis(4-aminophenyl)fluorene, 10mmol 4,4′-(4″,4′′′-dioxy-diphenylsulfone)- 1,1',8,8'-naphthalene tetracarboxylic dianhydride and 6mmol benzoic acid. First heat up to 100°C for 2h, then heat up to 200°C for 10h. After cooling, pour into 700mL acetone to obtain a fibrous solid , fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.44dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization: typical absorption peaks of imide ring: 1708cm ^-1 , 1669cm ^-1 , 1365cm ^-1 ; typical absorption peaks of sulfonic acid group: 1191cm ^-1 , 1027cm ^-1 .

The polymer obtained is a sulfonated polyimide random copolymer with the following general structural formula:

The dried polyimide powder was dissolved in N-methylpyrrolidone, and the solid content of the polymer was 10 wt.%. After the polymer was completely dissolved, it was filtered, and the obtained filtrate was cast into a film, dried in an oven at 80°C for 10 hours, and then dried at 120°C for 12 hours. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 50 μm and a conductivity of 0.04 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane maintains 96% compared with that before hydrolysis.

Example 15:

First, 6mmol 9,9'-bis(4-aminophenyl)fluorene-2,7'-disulfonic acid and 14mmol triethylamine were added to 60mL m-cresol, and 9,9'-bis(4-amino After phenyl)fluorene-2,7′-disulfonic acid is completely dissolved; add 4mmol 9,9′-bis(4-aminophenyl)fluorene, 10mmol 4,4′-(4″,4′′′-bis Mercaptobenzophenone)-1,1',8,8'-naphthalene tetracarboxylic dianhydride and 25mmol benzoic acid. First heat up to 100°C for 2h, then heat up to 180°C for 15h. Pour into 800mL acetone after cooling , to obtain a fibrous solid, fully washed and dried to obtain a polymer.

The comparative logarithmic viscosity of the prepared polymer is: 0.44dL/g (test conditions: test in m-cresol, temperature is 30°C; concentration is 0.5g/dL).

Infrared spectrum characterization of the prepared polymer: typical absorption peaks of imide ring: 1707cm ^-1 , 1667cm ^-1 , 1365cm ^-1 ; typical absorption peaks of sulfonic acid group: 1192cm ^-1 , 1021cm ^-1 .

The polymer obtained is a sulfonated polyimide random copolymer with the following general structural formula:

The obtained dry polyimide powder was dissolved in N-methylpyrrolidone, and the solid content of the polymer was 10 wt.%. After the polymer is completely dissolved, filter, pour the filtrate on a clean glass plate, dry at 80°C for 10h, and then dry at 120°C for 12h. Remove the film from the glass plate, then immerse it in ethanol and wash it thoroughly; then wash it fully with deionized water, put it in a sulfuric acid solution with a concentration of 2mol/L, keep it at room temperature for 1 day, and then wash it with a large amount of water , to obtain sulfonated polyimide proton exchange membrane. The proton exchange membrane has a thickness of 48 μm and a conductivity of 0.07 S/cm (70°C, 100% relative humidity); after hydrolysis in a high-pressure reactor at 140°C for 24 hours, the mechanical strength of the membrane maintains 90% of that before hydrolysis.

Claims (10)

1. hydrolyzation tolerant sulfonated polyimide; It is characterized in that one or more in the sulfonated polyimide segmented copolymer that described sulfonated polyimide is the sulfonated polyimide homopolymer be made up of structural unit shown in the formula I, be made up of structural unit shown in structural unit shown in the formula I and the formula II, the sulfonated polyimide random copolymers formed by structural unit shown in structural unit shown in the formula I and the formula II;

The molar content of structural unit is 2%-98% shown in the described sulfonated polyimide segmented copolymer Chinese style I;

The mol ratio of structural unit shown in structural unit and the formula II was more than or equal to 1: 9 shown in the described sulfonated polyimide random copolymers Chinese style I;

Wherein, X ₁Refer to a kind of residue, be

A kind of in the structure

X ₂Refer to a kind of residue, be

A kind of in the structure;

X ₁And X ₂Identical or different;

Ar ₁It is a kind of sulfonated diamine residue; Ar ₂It is a kind of common diamines residue.

2. hydrolyzation tolerant sulfonated polyimide according to claim 1 is characterized in that, described sulfonated diamine residue is any one in the following group:

3. hydrolyzation tolerant sulfonated polyimide according to claim 1 is characterized in that, described common diamines residue is any one in the following group:

4. hydrolyzation tolerant sulfonated polyimide according to claim 1 is characterized in that, described sulfonated polyimide be 0.30dL/g-2.00dL/g to logarithmic viscosity number.

5. the preparation method of hydrolyzation tolerant sulfonated polyimide according to claim 1 is characterized in that, the preparation method of described sulfonated polyimide homopolymer may further comprise the steps:

Sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection, add two naphthalene dianhydrides and catalyzer again; Be warming up to 60 ℃-100 ℃ reaction 1h-24h earlier, be warming up to 160 ℃-200 ℃ again and continue reaction 4h-48h, after the cooling solution is poured in the precipitation agent, collecting precipitation is after washing, and drying obtains the sulfonated polyimide homopolymer;

The preparation method of described sulfonated polyimide segmented copolymer may further comprise the steps:

(a) sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection, add two naphthalene dianhydrides again; Be warming up to 60 ℃-100 ℃ reaction 1h-24h earlier, be warming up to 160 ℃-200 ℃ again and continue reaction 4h-48h, obtain amino or the acid anhydride base is end capped and main chain contains sulfonic sulfonated polyamide acid oligomer body;

(b) common diamines and two naphthalene dianhydrides are dissolved in the phenol solvent of nitrogen protection, are warming up to 100 ℃-200 ℃ reaction 4h-48h, obtain the polyamic acid oligomer body of acid anhydride base or amine-terminated;

(c) the polyamic acid oligomer body in sulfonated polyamide acid oligomer body in the step (a) and the step (b) is mixed; Add catalyzer; Be warming up to 160 ℃-200 ℃ and continue reaction 4h-48h, after the cooling solution is poured in the precipitation agent, collecting precipitation is after washing; Drying obtains the sulfonated polyimide segmented copolymer;

The preparation method of described sulfonated polyimide random copolymers may further comprise the steps:

Sulfonated diamine and tertiary amine are dissolved in the phenol solvent of nitrogen protection; Add two naphthalene dianhydrides, common diamines and catalyzer again,, be warming up to 160 ℃-200 ℃ again and continue reaction 4h-48h to 60 ℃-100 ℃ reaction 1h-24h; After the cooling solution is poured in the precipitation agent; Collecting precipitation after the washing, drying obtains the sulfonated polyimide random copolymers.

6. the preparation method of hydrolyzation tolerant sulfonated polyimide according to claim 5 is characterized in that, described phenol solvent is one or more in phenol, meta-cresol, cresols, the P-Chlorophenol;

Described catalyzer is zinc chloride, phenylformic acid, isoquinoline 99.9, quinoline, triethylene diamine, benzyltrimethylammonium hydroxide, 1, one or more in the two dimethylamino naphthalenes of 8-;

Described precipitation agent is one or more in acetone, methyl alcohol, ethanol, the Virahol.

7. the preparation method of hydrolyzation tolerant sulfonated polyimide according to claim 5 is characterized in that, described tertiary amine is one or more among triethylamine, Tri-n-Propylamine, tri-n-butylamine, pyridine, the pyrroles;

Described tertiary amine is 2-3 with the ratio of the amount of substance of sulfonated diamine.

8. the application of hydrolyzation tolerant sulfonated polyimide according to claim 4 in preparation sulfonated polyimide matrix proton exchange.

9. application according to claim 8 is characterized in that, the described sulfonated polyimide proton exchange membrane electrolyte membrance in the battery that acts as a fuel.

10. application according to claim 9 is characterized in that, the preparation method of described sulfonated polyimide matrix proton exchange membrane material is:

Hydrolyzation tolerant sulfonated polyimide is dissolved in the solvent, and the solid content that obtains polymkeric substance is the solution of 2%-30%, filters; Gained filtrating at 60 ℃ of-120 ℃ of dry 10h-24h, again in 120 ℃ of-180 ℃ of dry 12h-24h, is immersed film in ethanol and the deionized water behind the thorough washing behind casting film-forming then successively; Put into the sulphuric acid soln that concentration is 0.5mol/L-4mol/L; Kept 1 day-7 days down at 20 ℃-60 ℃, water cleans then, obtains sulfonated polyimide matrix proton exchange.

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