CN107722271B - Preparation and application of side chain type sulfonated polyimide with quinoxaline group-containing main chain - Google Patents

Preparation and application of side chain type sulfonated polyimide with quinoxaline group-containing main chain Download PDF

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CN107722271B
CN107722271B CN201710981010.1A CN201710981010A CN107722271B CN 107722271 B CN107722271 B CN 107722271B CN 201710981010 A CN201710981010 A CN 201710981010A CN 107722271 B CN107722271 B CN 107722271B
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quinoxaline
bis
aminophenyl
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sulfonated polyimide
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CN107722271A (en
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王卫霞
陈康成
翟凤霞
房建华
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Nanjing black catalyst Co., Ltd.
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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The invention discloses side chain type sulfonated polyimide with a main chain containing quinoxaline groups, a preparation method thereof and a method for preparing a proton exchange membrane by using the side chain type sulfonated polyimide, wherein the side chain type sulfonated polyimide is structurally characterized in that the main chain contains quinoxaline groups, and ether bonds or thioether bonds on the quinoxaline groups are taken as connecting groups of side chains, so that the flexibility of the side chains and the hydrophobicity of the main chain are ensured, and the side chain type sulfonated polyimide has higher molecular weight, excellent thermal stability and good hydrolytic stability; the preparation method is simple in preparation process, easy to operate and control in reaction conditions and suitable for industrial production. The proton exchange membrane prepared by the side chain type sulfonated polyimide with the main chain containing quinoxaline groups has higher proton conductivity and excellent mechanical property, and has wide application prospect.

Description

Preparation and application of side chain type sulfonated polyimide with quinoxaline group-containing main chain
Technical Field
The invention relates to the field of high polymer materials, in particular to a preparation method of side chain type sulfonated polyimide with a main chain containing quinoxaline groups and a preparation method of a proton exchange membrane thereof.
Background
The sulfonated polyimide has the advantages of good physical and chemical stability, heat resistance, higher proton conductivity, easy preparation, low price and the like, and is considered to be a proton exchange membrane fuel cell material with great development prospect. However, the imide ring of such polymers is susceptible to attack by nucleophiles, resulting in poor hydrolytic stability. The water resistance can be improved by changing the monomer structure, and the introduction of a side chain type sulfonated diamine monomer is a very effective method. The literature (ECSTransactions 2008, 12, 5) reports a side-chain sulfonated polyimide linked by an ether bond, which polymer has excellent hydrolytic stability (maintaining mechanical strength in pressurized water at 130 ℃ for 500h or more). The literature (Journal of power Sources 2011, 196, 1694) reports a preparation method of a proton exchange membrane using quinoxaline as a crosslinking group, wherein a quinoxaline structure is introduced to a side chain of a polymer, so that the side chain structure is not beneficial to enhancing the flexibility of a high molecular chain.
Disclosure of Invention
In order to solve the technical problems, the invention provides side chain type sulfonated polyimide with a main chain containing quinoxaline groups, a preparation method thereof and a method for preparing a proton exchange membrane by using the side chain type sulfonated polyimide with the main chain containing quinoxaline groups. Quinoxaline groups are introduced to the main chain of polymer molecules, and ether bonds or thioether bonds are taken as connecting groups, so that the flexibility of side chains is ensured, and the proton conductivity of the polymer membrane can be increased.
The technical scheme of the invention is realized as follows:
a side chain type sulfonated polyimide having a quinoxaline group in the main chain thereof, comprising a sulfonated polyimide homopolymer (y ═ 1) or a sulfonated polyimide copolymer (0 < y < 1) having the general formula (I):
Figure BDA0001438994010000021
wherein X represents O or S;
wherein R is1-(SO3H)aThe method comprises the following steps:
Figure BDA0001438994010000022
R2the method comprises the following steps:
Figure 1
R3the method comprises the following steps:
Figure BDA0001438994010000031
n is a positive integer; a is 1 or 2 or 3; y is more than 0 and less than or equal to 1.
A preparation method of side chain type sulfonated polyimide with a main chain containing quinoxaline groups comprises a preparation method of sulfonated polyimide homopolymer (y is 1) and a preparation method of sulfonated polyimide copolymer (y is more than 0 and less than 1), wherein the preparation method of the sulfonated polyimide homopolymer (y is 1) comprises the following steps:
under the protection of nitrogen, dissolving sulfonated diamine and a certain amount of organic weak base in an organic solvent, then adding a dianhydride monomer and a certain amount of organic weak acid which are equimolar with the sulfonated diamine, reacting the reaction system at 80-140 ℃ for 1-8h, then reacting at 160-220 ℃ for 8-24h, after the reaction is finished, reducing the temperature of the system to 70-120 ℃, then pouring the system into methanol to obtain a filamentous product, repeatedly washing and drying in a vacuum oven to obtain the sulfonated polyimide homopolymer;
the preparation method of the sulfonated polyimide copolymer (y is more than 0 and less than 1) comprises the following steps:
under the protection of nitrogen, dissolving sulfonated diamine, non-sulfonated diamine and a certain amount of organic weak base in an organic solvent, adding dianhydride monomer and organic weak acid in the same molar amount as diamine (the total amount of the sulfonated diamine and the non-sulfonated diamine), reacting the reaction system at 80-140 ℃ for 1-8h, reacting at 160-220 ℃ for 8-24h, cooling the system to 70-120 ℃ after the reaction is finished, pouring into methanol to obtain a filamentous product, repeatedly washing and drying in a vacuum oven to obtain the sulfonated polyimide copolymer.
Further, the sulfonated diamine is 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -benzenesulfonic acid, 5- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -2-methylbenzenesulfonic acid, 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -1, 3-benzenedisulfonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -5- (4-sulfo-thiophenyl) benzenesulfonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -5- (4-sulfo-phenoxy) benzenesulfonic acid, 4- {4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3-sulfonic acid-phenoxy } -1, 3-benzenedisulfonic acid, 4- {4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3-sulfonic acid-phenylthio } -1, 3-benzenedisulfonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -5- [ 1-methyl-1- (4-sulfophenyl) ethyl ] benzenesulfonic acid, 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3, 4' -disulfonated biphenyl, 2- [2, 3-bis- (4-aminophenyl) -quinoxaline-6-oxy ] -5- (4-sulfonic-benzyl) -benzenesulfonic acid, 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -benzenesulfonic acid, 5- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -2-methylbenzenesulfonic acid, 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -1, 3-benzenedisulfonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -5- (4-sulfonic-phenylthio) benzenesulfonic acid 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -5- (4-sulfo-phenoxy) benzenesulphonic acid, 4- {4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -3-sulfo-phenoxy } -1, 3-benzenedisulphonic acid, 4- {4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -3-sulfo-phenylthio } -1, 3-benzenedisulphonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -5- [ 1-methyl-1- (4-sulphophenyl) ethyl ] benzenesulphonic acid And 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -3, 4' -disulfonic acid biphenyl, 2- [2, 3-bis- (4-aminophenyl) -quinoxaline-6-thio ] -5- (4-sulfonic acid-benzyl) benzene sulfonic acid.
Further, the non-sulfonated diamine is 4,4 '-diaminodiphenyl ether, 1, 4-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4' -bis (4-aminophenoxy) biphenyl, 3 '-dimethyl-4, 4' -diaminobiphenyl, 2 '-dimethyl-4, 4' -diaminobiphenyl, 2, 2-bis (4-aminophenyl) propane, 2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl, 4 '-diaminodiphenylmethane, bis (3-methyl-4-aminophenyl) methane, bis (3, 5-dimethyl-4-aminophenyl) methane, 9' -bis (4-aminophenyl) fluorene.
Further, the dianhydride monomer is one of 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 4 '-binaphthyl-1, 1', 8,8 '-tetracarboxylic dianhydride, 4' -dinaphthylether-1, 1 ', 8, 8' -tetracarboxylic dianhydride, 4 '-dinaphthone-1, 1', 8,8 '-tetracarboxylic dianhydride, biphenyl-4, 4' -bis (4-oxo-1, 8-naphthalic anhydride) and perylene-3, 4,9, 10-tetracarboxylic dianhydride.
Further, the organic weak base is one of triethylamine, triethylene diamine, pyridine, N-methylmorpholine and isoquinoline; the organic weak acid is one of formic acid, acetic acid, benzoic acid, phenylacetic acid and oxalic acid; the organic solvent is one of m-cresol, 1-methyl pyrrolidone and N, N-dimethyl acetamide.
Further, the mol adding amount of the organic weak base is 2.0-4.0 times of the adding amount of the sulfonated diamine; the mol adding amount of the organic weak acid is 1.0-3.0 times of the adding amount of the dianhydride monomer.
Further, the total mass concentration of the sulfonated diamine, the non-sulfonated diamine and the dianhydride monomer in the organic solvent is 8-20%.
The invention also provides a method for preparing a proton exchange membrane by using the side chain type sulfonated polyimide with the main chain containing quinoxaline groups, which comprises the following steps:
dissolving side chain type sulfonated polyimide with a main chain containing quinoxaline groups in an organic solvent, pouring the solution on a clean glass plate after filtering, drying the solution for 2 to 8 hours in a blast oven at 60 to 120 ℃, fully washing the obtained membrane in ethanol, soaking the membrane in a hydrochloric acid solution with the temperature of 60 to 90 ℃ and the concentration of 1.5 to 4.0mol/L for 4 to 24 hours, washing the membrane with deionized water to be neutral, and drying the membrane to obtain the side chain type sulfonated polyimide proton exchange membrane with the main chain containing quinoxaline groups.
Further, the organic solvent is one of m-cresol, 1-methyl pyrrolidone and N, N-dimethyl acetamide.
Further, the mass concentration of the side chain type sulfonated polyimide with the main chain containing quinoxaline groups in the organic solvent is 2-20%.
The invention has the beneficial effects that: the invention provides side chain type sulfonated polyimide, wherein a main chain contains quinoxaline groups, and ether bonds or thioether bonds on the quinoxaline groups are taken as connecting groups of side chains, so that the flexibility of the side chains and the hydrophobicity of the main chain are ensured, and the side chain type sulfonated polyimide also has higher molecular weight, excellent thermal stability and good hydrolytic stability; the preparation method of the side chain type sulfonated polyimide with the main chain containing quinoxaline groups has simple process and easily controlled reaction conditions, and the obtained polymer can be used for preparing the proton exchange membrane with excellent performance. The proton exchange membrane prepared by the side chain type sulfonated polyimide with the main chain containing quinoxaline groups has higher proton conductivity, excellent mechanical property and thermal stability, and is a proton exchange membrane material with wide application prospect.
Drawings
FIG. 1 is a scheme for the synthesis of side chain sulfonated polyimides containing quinoxaline groups in a preferred embodiment of the present invention;
FIG. 2 is an infrared spectrum of a side chain type sulfonated polyimide containing quinoxaline groups in a preferred embodiment of the present invention;
FIG. 3 is a graph showing the thermogravimetric curve of side chain type sulfonated polyimide containing quinoxaline groups in a preferred embodiment of the present invention.
Detailed Description
In order to clearly understand the technical contents of the present invention, the following examples are given in detail for the purpose of better understanding the contents of the present invention and are not intended to limit the scope of the present invention.
The invention provides side chain type sulfonated polyimide with a main chain containing quinoxaline groups, which comprises a sulfonated polyimide homopolymer (y is 1) or a sulfonated polyimide copolymer (y is more than 0 and less than 1) with a general formula (I):
Figure BDA0001438994010000061
wherein X represents O or S;
wherein R is1-(SO3H)aComprises that：
Figure BDA0001438994010000062
R2The method comprises the following steps:
Figure 2
R3the method comprises the following steps:
Figure BDA0001438994010000071
n is a positive integer; a is 1 or 2 or 3; y is more than 0 and less than or equal to 1.
The invention also provides a preparation method of the side chain type sulfonated polyimide with a main chain containing quinoxaline groups, which comprises a preparation method of a sulfonated polyimide homopolymer (y is 1) and a preparation method of a sulfonated polyimide copolymer (0 < y < 1), wherein the synthetic route of the preparation method is shown as figure 1, and the preparation method of the sulfonated polyimide homopolymer (y is 1) comprises the following steps:
under the protection of nitrogen, dissolving sulfonated diamine and a certain amount of organic weak base in an organic solvent, then adding a dianhydride monomer and a certain amount of organic weak acid which are equimolar with the sulfonated diamine, reacting the reaction system at 80-140 ℃ for 1-8h, then reacting at 160-220 ℃ for 8-24h, after the reaction is finished, reducing the temperature of the system to 70-120 ℃, then pouring the system into methanol to obtain a filamentous product, repeatedly washing and drying in a vacuum oven to obtain the sulfonated polyimide homopolymer;
the preparation method of the sulfonated polyimide copolymer (y is more than 0 and less than 1) comprises the following steps:
under the protection of nitrogen, dissolving sulfonated diamine, non-sulfonated diamine and a certain amount of organic weak base in an organic solvent, adding dianhydride monomer and organic weak acid in the same molar amount as diamine (the total amount of the sulfonated diamine and the non-sulfonated diamine), reacting the reaction system at 80-140 ℃ for 1-8h, reacting at 160-220 ℃ for 8-24h, cooling the system to 70-120 ℃ after the reaction is finished, pouring into methanol to obtain a filamentous product, repeatedly washing and drying in a vacuum oven to obtain the sulfonated polyimide copolymer.
The invention also provides a method for preparing a proton exchange membrane by using the side chain type sulfonated polyimide with the main chain containing quinoxaline groups, which comprises the following steps:
dissolving side chain type sulfonated polyimide with a main chain containing quinoxaline groups in an organic solvent, pouring the solution on a clean glass plate after filtering, drying the solution in a blast oven at 60-120 ℃ for 2-8h, fully washing the obtained membrane in ethanol, soaking the membrane in a hydrochloric acid solution with the temperature of 60-90 ℃ and the concentration of 1.5-4.0mol/L for 4-24h, washing the membrane with deionized water to be neutral, and drying the membrane to obtain the side chain type sulfonated polyimide proton exchange membrane containing the quinoxaline groups.
The following will describe in detail the preparation of side chain type sulfonated polyimide having quinoxaline groups in the main chain by specific examples:
example 1: the synthesis of side chain type sulfonated polyimide homopolymer with a main chain containing quinoxaline groups and the preparation of a proton exchange membrane:
4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3, 4' -disulfonated biphenyl 6.401g (10mmol), triethylamine 2.024-4.048g (20-40mmol) and m-cresol 45-115mL are added to a 250mL dry three-necked flask under nitrogen protection and mechanical stirring, preferably with the optimum amounts in the present example being 3.036g (30mmol) and 75mL, respectively. After complete dissolution, 2.682g of 1,4,5, 8-naphthalene tetracarboxylic dianhydride (10mmol) and 1.221-3.664g of benzoic acid (10-30mmol) are added, preferably 2.907g (23.8mmol) is the most preferred amount in this example. Under the protection of nitrogen, the reaction system is firstly heated to 80-140 ℃ for reaction for 1-8h, and then is continuously heated to 160-220 ℃ for reaction for 8-24h, preferably, the two temperatures in the embodiment are respectively 100 ℃ and 180 ℃, and the two times are respectively 4h and 20 h. After the reaction is finished, cooling the system to 110 ℃, pouring the product solution into 500mL of methanol, washing the obtained fibrous product for 3-5 times by using the methanol, and drying at 120 ℃ in vacuum for later use.
The sulfonated polyimide obtained in the experiment is dissolved in m-cresol to prepare a solution with the mass concentration of 2-15%, preferably, the optimal mass concentration in the embodiment is 10%. After filtration, the solution was poured onto a clean glass plate and dried in a forced air oven at 60-120 ℃ for 2-8h, the temperatures and times used in this example were 100 ℃ and 4h, respectively. The dried membrane is fully washed in ethanol, and then soaked in hydrochloric acid solution with the temperature of 60-90 ℃ and the concentration of 1.5-4.0mol/L for 4-24h, preferably, the conditions adopted in the embodiment are 80 ℃, 3mol/L and 10h respectively. Then washing the membrane with deionized water to be neutral and drying the membrane to obtain the side chain type sulfonated polyimide proton exchange membrane with the main chain containing quinoxaline groups.
Example 2: the synthesis of side chain type sulfonated polyimide copolymer with a main chain containing quinoxaline groups and the preparation of a proton exchange membrane:
3.201g (5mmol) of 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3, 4' -disulfonic acid biphenyl were added to a 250mL dry three-necked flask under the protection of nitrogen and with mechanical stirring, in this example the optimum amounts of triethylamine added being 1.619g (16mmol) and 60mL of m-cresol, respectively. After the solution was completely dissolved, 1.001g (5mmol) of 4, 4' -diaminodiphenyl ether and 2.682g (10mmol) of 1,4,5, 8-naphthalenetetracarboxylic dianhydride were added, and the optimum amount of benzoic acid added in this example was 2.198g (18 mmol).
The rest of the experimental procedure was the same as in example 1.
The proton exchange membrane was prepared in the same manner as in example 1.
Example 3: the synthesis of side chain type sulfonated polyimide copolymer with a main chain containing quinoxaline groups and the preparation of a proton exchange membrane:
5.121g (8mmol) of 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3, 4' -disulfonic acid biphenyl were added to a 250mL dry three-necked flask under the protection of nitrogen and with mechanical stirring, in this example the optimum amounts of triethylamine being 2.267g (22.4mmol) and 90mL of m-cresol. After the solution was completely dissolved, 0.801g (4mmol) of 4, 4' -diaminodiphenyl ether and 3.218g (12mmol) of 1,4,5, 8-naphthalene tetracarboxylic dianhydride were added, and the optimum amount of benzoic acid added in this example was 2.931g (24 mmol).
The rest of the experimental procedure was the same as in example 1.
The proton exchange membrane was prepared in the same manner as in example 1.
Example 4: the synthesis of side chain type sulfonated polyimide copolymer with a main chain containing quinoxaline groups and the preparation of a proton exchange membrane:
3.201g (5mmol) of 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3, 4' -disulfonic acid biphenyl were added to a 250mL dry three-necked flask under the protection of nitrogen and with mechanical stirring, in this example the optimum amounts of triethylamine being 1.518g (15mmol) and 50mL of m-cresol, respectively. After the reaction solution was completely dissolved, 1.842g (5mmol) of 4, 4' -bis (4-aminophenoxy) biphenyl and 2.682g (10mmol) of 1,4,5, 8-naphthalene tetracarboxylic dianhydride were added, and the optimum amount of benzoic acid added in this example was 1.832g (15 mmol).
The rest of the experimental procedure was the same as in example 1.
The proton exchange membrane was prepared in the same manner as in example 1.
Example 5: the synthesis of side chain type sulfonated polyimide copolymer with a main chain containing quinoxaline groups and the preparation of a proton exchange membrane:
2.907g (6mmol) of 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] benzenesulfonic acid were introduced into a 250mL dry three-necked flask under nitrogen protection and mechanical stirring, in this example the optimum amounts of triethylamine were 1.396g (13.8mmol) and 70mL of m-cresol, respectively. After the solution was completely dissolved, 1.201g (6mmol) of 4, 4' -diaminodiphenyl ether and 3.218g (12mmol) of 1,4,5, 8-naphthalene tetracarboxylic dianhydride were added, and the optimum amount of benzoic acid added in this example was 3.054g (25 mmol).
The rest of the experimental procedure was the same as in example 1.
The proton exchange membrane was prepared in the same manner as in example 1.
Example 6: the synthesis of side chain type sulfonated polyimide copolymer with a main chain containing quinoxaline groups and the preparation of a proton exchange membrane:
3.201g (5mmol) of 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3, 4' -disulfonic acid biphenyl were added to a 250mL dry three-necked flask under the protection of nitrogen and with mechanical stirring, in this example the optimum amounts of triethylamine being 2.315g (13mmol) and 75mL of m-cresol. After complete dissolution, 1.001g (5mmol) of 4, 4' -diaminodiphenyl ether and 3.923g (10mmol) of perylene 3,4,9, 10-tetracarboxylic dianhydride were added, and the optimum amount of benzoic acid added in this example was 1.831g (15 mmol).
The rest of the experimental procedure was the same as in example 1.
The proton exchange membrane was prepared in the same manner as in example 1.
The following table 1 shows the proton conductivity results of the proton exchange membranes prepared by using the side chain type sulfonated polyimide with quinoxaline group containing main chain prepared in 6 preferred embodiments of the present invention in water at different temperatures, and the results in table 1 show that the proton exchange membranes all have higher proton conductivity.
TABLE 1
Figure BDA0001438994010000101
FIG. 2 is an infrared spectrum (proton state) of a side chain type sulfonated polyimide containing quinoxaline groups according to 6 preferred embodiments of the present invention, wherein 1710cm is-1And 1670cm-1The peaks at the left and right are characteristic absorption peaks of imide ring, 1090cm-1And 1017cm-1The left and right peaks are characteristic absorption peaks of sulfonic acid group, 1500cm-1The left and right peaks are proton absorption peaks of quinoxaline ring, wherein 1670cm-1The peak broadening at (b) is caused by the fact that C ═ N on the quinoxaline ring is almost the same as the absorption peak position of the main chain C ═ 0. As can be seen from the figure, the preparation method provided by the invention can successfully obtain the side chain type sulfonated polyimide with the main chain containing quinoxaline groups.
FIG. 3 is a thermogravimetric curve (proton state) of side chain type sulfonated polyimide containing quinoxaline groups according to 6 preferred embodiments of the present invention, in which the thermogravimetric loss from room temperature to 150 ℃ is due to volatilization of moisture, the thermogravimetric loss from 300 ℃ to 450 ℃ is due to decomposition of sulfonic acid groups, and the thermogravimetric loss above 500 ℃ is due to degradation of the main chain of the polymer. As can be seen, the polymer still has over 30 percent of ash residue at the temperature of 700 ℃, which shows that the polymer has excellent thermal stability.
In summary, the invention provides side chain type sulfonated polyimide with a main chain containing quinoxaline groups, a preparation method thereof and a method for preparing a proton exchange membrane by using the side chain type sulfonated polyimide, and the side chain type sulfonated polyimide is structurally characterized in that a side chain with a sulfonic group takes an ether bond or a thioether bond of the quinoxaline group on the main chain as a bridging group, thereby not only increasing the hydrophobicity of the main chain, but also ensuring the flexibility of the side chain. The preparation method is easy to operate and control, is suitable for industrial production, and the prepared sulfonated polyimide has higher molecular weight and good hydrolytic stability, and has wide application prospect in the field of proton exchange membranes.
The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, and those skilled in the art will be able to make various changes and modifications to the embodiments without departing from the spirit of the invention.

Claims (11)

1. A side chain type sulfonated polyimide having a main chain containing quinoxaline groups, characterized in that the sulfonated polyimide is a sulfonated polyimide homopolymer having the general formula (I) wherein y is 1, or a sulfonated polyimide copolymer wherein 0< y < 1:
Figure FDA0002394040840000011
wherein X represents O or S;
wherein R1- (SO3H) a comprises:
Figure FDA0002394040840000012
r2 includes:
Figure FDA0002394040840000013
r3 includes:
Figure FDA0002394040840000021
n is a positive integer; a is 1 or 2 or 3; y is more than 0 and less than or equal to 1.
2. A method for preparing a side chain type sulfonated polyimide having a quinoxaline group in the main chain according to claim 1, wherein the sulfonated polyimide homopolymer is a sulfonated polyimide homopolymer, wherein y is 1, which comprises the steps of:
under the protection of nitrogen, dissolving sulfonated diamine and a certain amount of organic weak base in an organic solvent, then adding a dianhydride monomer and a certain amount of organic weak acid which are equimolar with the sulfonated diamine, reacting the reaction system at 80-140 ℃ for 1-8h, then reacting at 160-220 ℃ for 8-24h, after the reaction is finished, reducing the temperature of the system to 70-120 ℃, then pouring the system into methanol to obtain a filamentous product, repeatedly washing and drying in a vacuum oven to obtain the sulfonated polyimide homopolymer;
the sulfonated polyimide copolymer, wherein 0< y <1, is prepared by the following steps:
under the protection of nitrogen, dissolving sulfonated diamine, non-sulfonated diamine and a certain amount of organic weak base in an organic solvent, adding a dianhydride monomer and a certain amount of organic weak acid which are equimolar with the total amount of the sulfonated diamine and the non-sulfonated diamine, reacting the reaction system at 80-140 ℃ for 1-8h, then reacting at 160-220 ℃ for 8-24h, cooling the system to 70-120 ℃ after the reaction is finished, pouring into methanol to obtain a filamentous product, repeatedly washing and drying in a vacuum oven to obtain the sulfonated polyimide copolymer.
3. The method for producing a side chain type sulfonated polyimide having a quinoxaline group in the main chain according to claim 2, wherein the sulfonated diamine is 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -benzenesulfonic acid, 5- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -2-methylbenzenesulfonic acid, 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -1, 3-benzenedisulfonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -5- (4-sulfo-phenylthio) benzenesulfonic acid, or a mixture thereof, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -5- (4-sulfo-phenoxy) benzenesulphonic acid, 4- {4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3-sulfo-phenoxy } -1, 3-benzenedisulphonic acid, 4- {4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3-sulfo-phenylthio } -1, 3-benzenedisulphonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -5- [ 1-methyl-1- (4-sulfophenyl) ethyl ] benzenesulphonic acid, processes for their preparation, pharmaceutical compositions containing them and their use, 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-oxy ] -3, 4' -disulfonylbiphenyl, 2- [2, 3-bis- (4-aminophenyl) -quinoxaline-6-oxy ] -5- (4-sulfonic acid-benzyl) benzenesulfonic acid, 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -benzenesulfonic acid, 5- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -2-methylbenzenesulfonic acid, 4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -1, 3-benzenedisulfonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -5- (4-sulfo-phenylthio) benzenesulfonic acid, 2- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -5- (4-sulfo-phenoxy) benzenesulfonic acid, 4- {4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -3-sulfo-phenoxy } -1, 3-benzenedisulfonic acid, 4- {4- [2, 3-bis (4-aminophenyl) -quinoxaline-6-thio ] -3-sulfo-phenylthio } -1, 3-benzene disulfonic acid, 2- [2, 3-di (4-aminophenyl) -quinoxaline-6-thio ] -5- [ 1-methyl-1- (4-sulfophenyl) ethyl ] benzenesulfonic acid, 4- [2, 3-di (4-aminophenyl) -quinoxaline-6-thio ] -3, 4' -disulfonic acid biphenyl, 2- [2, 3-di- (4-aminophenyl) -quinoxaline-6-thio ] -5- (4-sulfonic acid-benzyl) benzenesulfonic acid.
4. The method for producing a side chain type sulfonated polyimide having a quinoxaline group in the main chain according to claim 2, wherein the non-sulfonated diamine is 4,4 ' -diaminodiphenyl ether, 1, 4-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, 4 ' -bis (4-aminophenoxy) biphenyl, 3 ' -dimethyl-4, 4 ' -diaminobiphenyl, 2-bis (4-aminophenyl) propane, 2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl, 4 ' -diaminodiphenylmethane, bis (3-methyl-4-aminophenyl) methane, bis (4-aminophenoxy) benzene, or bis (4-aminophenoxy) benzene, One of bis (3, 5-dimethyl-4-aminophenyl) methane and 9, 9' -bis (4-aminophenyl) fluorene.
5. The method for preparing a side chain type sulfonated polyimide having a main chain containing quinoxaline groups according to claim 2, wherein the dianhydride monomer is one of 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 4 '-binaphthyl-1, 1', 8,8 '-tetracarboxylic dianhydride, 4' -dinaphthylether-1, 1 ', 8, 8' -tetracarboxylic dianhydride, 4 '-dinaphthone-1, 1', 8,8 '-tetracarboxylic dianhydride, biphenyl-4, 4' -bis (4-oxo-1, 8-naphthalic anhydride), perylene-3, 4,9, 10-tetracarboxylic dianhydride.
6. The method for preparing side chain type sulfonated polyimide containing quinoxaline group in main chain according to claim 2, wherein the weak organic base is one of triethylamine, triethylenediamine, pyridine, N-methylmorpholine and isoquinoline; the organic weak acid is one of formic acid, acetic acid, benzoic acid, phenylacetic acid and oxalic acid; the organic solvent is one of m-cresol, 1-methyl pyrrolidone and N, N-dimethyl acetamide.
7. The method for preparing side chain type sulfonated polyimide having a main chain containing quinoxaline groups according to claim 2, wherein the molar addition amount of the weak organic base is 2.0 to 4.0 times of the addition amount of the sulfonated diamine; the molar addition amount of the organic weak acid is 1.0-3.0 times of the addition amount of the dianhydride monomer.
8. The method for preparing side chain type sulfonated polyimide having quinoxaline groups in the main chain according to claim 2, wherein the total mass concentration of the sulfonated diamine, non-sulfonated diamine and dianhydride monomers in the organic solvent is 8 to 20%.
9. A method for preparing a proton exchange membrane by using side chain type sulfonated polyimide with a main chain containing quinoxaline groups is characterized by comprising the following steps: dissolving the side chain type sulfonated polyimide with a quinoxaline group-containing main chain in an organic solvent, pouring the solution on a clean glass plate after filtering, drying the solution for 2 to 8 hours in a blast oven at 60 to 120 ℃, fully washing the obtained membrane in ethanol, soaking the membrane in a hydrochloric acid solution with the temperature of 60 to 90 ℃ and the concentration of 1.5 to 4.0mol/L for 4 to 24 hours, washing the membrane with deionized water to be neutral, and drying the membrane to obtain the side chain type sulfonated polyimide proton exchange membrane with the quinoxaline group-containing main chain.
10. The method for preparing a proton exchange membrane by using the side chain type sulfonated polyimide containing quinoxaline groups on the main chain according to claim 9, wherein the organic solvent is one of m-cresol, 1-methylpyrrolidone and N, N-dimethylacetamide.
11. The method for preparing a proton exchange membrane by using the side chain type sulfonated polyimide containing quinoxaline groups on the main chain according to claim 9, wherein the mass concentration of the side chain type sulfonated polyimide containing quinoxaline groups on the main chain in an organic solvent is 2-20%.
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