CN102728237A - Homogeneous anion exchange membrane and preparation method thereof - Google Patents

Abstract

The invention discloses a homogeneous anion exchange membrane and a preparation method thereof. The method comprises the following steps: dissolving a halomethylated aromatic high polymer in an organic solvent to form a solution to be reacted; dissolving the solution to be reacted Mixing with thiazole functional small molecules and performing nucleophilic substitution reaction to obtain a casting solution of aromatic polymers with positively charged thiazole functional small molecule side groups; and casting the casting solution on the substrate The film is coated and dried, after which the substrate is removed, or the casting solution is coated on a reinforcing fabric and dried, resulting in a homogeneous anion exchange membrane.

Description

Homogeneous anion exchange membrane and preparation method thereof

technical field

The invention relates to the technical field of membranes, in particular to a homogeneous anion exchange membrane and a preparation method thereof.

Background technique

Since anion exchange membranes are widely used in seawater (brackish water) desalination, tap water dehardening, electrodialysis, diffusion dialysis, electrochemical sensing and fuel cells, their use and development have always attracted people's attention. The homogeneous anion exchange membrane has the advantages of uniform structure, low resistance and stable performance, and has applications in the fields of electrodialysis and fuel cells.

The Netherlands "Journal of Membrane Science and Technology" (Journal of Membrane Science, 2001, 190, 159-166) reported a method for preparing an anion exchange membrane by modifying polyphenylene ether. group, soaked in trimethylamine aqueous solution for 48h after film formation to obtain anion exchange membrane.

The Netherlands "Journal of Membrane Science and Technology" (Journal of Membrane Science, 2005, 262, 1-4) reported a method for preparing an anion exchange membrane by modifying polyethersulfone with phenolphthalein side groups. The base polyethersulfone is equipped with chloromethyl groups, and soaked in an aqueous solution of trimethylamine for 48 hours after film formation to obtain an anion exchange membrane.

The Netherlands "Journal of Power Sources" (journal of power sources, 2009, 193, 541-546) reported a method for preparing an anion exchange membrane by modifying polyether ketone with phenolphthalein side groups. The ketone carries chloromethyl groups, and after film formation, it is immersed in an aqueous solution of trimethylamine for 48 hours to obtain an anion exchange membrane.

The method for preparing the anion exchange membrane above is to obtain the base membrane after halomethylation of the polymer, and then soak the base membrane in an aqueous solution of trimethylamine for quaternization reaction to obtain an anion exchange membrane containing quaternary ammonium groups. Since the reaction between the two takes place between the solid base film and the liquid trimethylamine aqueous solution, it is a heterogeneous reaction. This heterogeneous reaction has the following two disadvantages: one, the amount of trimethylamine aqueous solution used to soak the basement membrane is very large, which causes waste of trimethylamine aqueous solution and increases the cost; two, because the basement membrane is in the It has been solidified before the quaternization reaction with trimethylamine, so the membrane lacks the driving force for hydrophobic and hydrophilic phase separation during the introduction of quaternary ammonium groups, and cannot form a penetrating ion channel in the membrane, which reduces the anion exchange rate of the final preparation. In addition, trimethylamine is a highly volatile gas with a fishy odor, which has a strong irritating effect on the eyes, nose, throat and respiratory tract of the human body. At the same time, the quaternary ammonium group obtained by the reaction of trimethylamine and halomethyl group is unstable under alkaline conditions and will be degraded to a large extent. The above disadvantages have limited the large-scale application of the anion exchange membrane prepared by the above method.

Contents of the invention

In view of this, the technical problem to be solved by the present invention is to provide a homogeneous anion exchange membrane and a preparation method thereof, so as to overcome the above disadvantages.

The invention provides a kind of preparation method of homogeneous anion exchange membrane, described method comprises the following steps:

Dissolving the halomethylated aromatic polymer in an organic solvent to form a solution to be reacted;

Mixing the solution to be reacted with the thiazole functional small molecule and performing a nucleophilic substitution reaction to obtain a casting solution of an aromatic polymer with a positively charged thiazole functional small molecule side group; and The casting solution is coated on a substrate and dried, after which the substrate is removed, or the casting solution is coated on a reinforcing fabric and dried, resulting in a homogeneous anion exchange membrane.

Preferably, the halomethylated aromatic high polymer is halomethylated polyphenylsulfone, polyethersulfone, bisphenol A polysulfone, polyether ether ketone, polyether ketone, polyphenylene ether, heteronaphthalene Biphenyl polyether sulfone, polynaphthalene polyether sulfone, polynaphthalene polyether sulfone ketone, polyarylether ketone with phenolphthalein side groups, or polyarylether sulfone with phenolphthalein side groups, which are composed of corresponding aromatic Polymers are obtained by halomethylation, wherein the molar ratio of repeating units containing halomethyl groups to all repeating units is called their degree of halomethylation. Taking halomethylated polyethersulfone as an example, it The structural formula is as follows:

The degree of halomethylation of polyethersulfone refers to the molar ratio of repeating units containing chloromethyl groups to all repeating units in polyethersulfone, that is, n in the above structural formula.

Preferably, the halomethylation degree of the aromatic high polymer is 20mol%-100mol%.

Preferably, the organic solvent is any one of toluene, chlorobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone or a mixture thereof.

The mass volume concentration of the solution to be reacted may be 1-50 m/v%.

Preferably, the thiazole functional small molecule has a structure represented by the following formula:

Wherein R ₁ , R ₂ , and R ₃ are each independently H or an alkyl segment.

Preferably, the molar ratio of the halomethyl group contained in the halomethylated aromatic polymer to the thiazole functional small molecule may be 1:0.2-3.

Preferably, the reaction temperature of the halomethylated aromatic polymer and the thiazole functional small molecule can be 0°C to 130°C, and the reaction time can be 1-48h.

Preferably, the substrate is a polytetrafluoroethylene plate, polyethylene film, glass plate, aluminum plate or stainless steel plate. The reinforcing fabric can be polyethylene cloth, polypropylene cloth, nylon cloth, polyester cloth or nylon cloth.

Preferably, the coating is performed by casting, doctor blade, spraying, dipping, flow or spin coating.

Drying can be carried out by volatilizing at room temperature or heating and drying at 25-130°C.

The present invention also provides a homogeneous anion exchange membrane, the homogeneous anion exchange membrane includes a cast film layer, wherein the cast film layer is made of an aromatic polymer with a positively charged thiazole functional small molecule side group The aromatic high polymer with positively charged thiazole functional small molecule side groups is the nucleophilic substitution reaction product of halomethylated aromatic high polymer and thiazole functional small molecule. The aromatic polymer with positively charged thiazole functional small molecular side groups has a cationic part and an anionic part (halide ion), and the cationic part is composed of a halomethylated aromatic polymer main chain and Positively charged thiazole functional small molecular side groups. Taking polyethersulfone with positively charged thiazole functional small molecule side groups as an example, its chemical structural formula is:

Among them, n is the degree of halomethylation of polyethersulfone, and its size is 20-100mol%, and x is the proportion of halomethyl groups reacting with thiazole functional small molecules in halomethylated polyethersulfone. The molar ratio of the group, its size is 20-100mol%, wherein R ₁ , R ₂ , R ₃ are each independently H or an alkyl segment.

According to the homogeneous anion exchange membrane of the present invention, the halomethylated aromatic high polymer is preferably halomethylated polyphenylsulfone, polyethersulfone, bisphenol A polysulfone, polyether ether ketone, polyether Ketones, polyphenylene ethers, polynaphthalene polyethersulfones, polynaphthalene polyethersulfones, polyarylether ketones with phenolphthalein side groups, or polyarylethers with phenolphthalein side groups sulfone.

According to the homogeneous anion exchange membrane of the present invention, the positively charged thiazole functional small molecule side group has a structure represented by the following formula:

Wherein R ₁ , R ₂ , and R ₃ are each independently H or alkyl.

According to the homogeneous anion exchange membrane of the present invention, the homogeneous anion exchange membrane also includes a reinforcing fabric positioned under the cast film layer, and the reinforcing fabric is polyethylene cloth, polypropylene cloth, nylon cloth, polyester cloth or nylon cloth.

The water content of the anion exchange membrane is 2-130%, the ion exchange capacity is 0.1-2.7mmolg ^-1 , the ion conductance is 1-30mS cm ^-1 , and the mechanical strength is preferably 10-60MPa.

Since high polymers and functional small molecules can be dissolved in a single organic solvent and react simultaneously, the anion exchange membrane prepared in the present invention is a homogeneous membrane. By adopting the method of the present invention, the properties of the anion exchange membrane can be controlled by controlling the degree of halomethylation of the polymer and the molar ratio between the halomethyl group and the thiazole functional small molecule, thereby selecting the suitable water content and higher ion exchange content, excellent ion conductivity and alkali-resistant homogeneous anion exchange membrane. Compared with the prior art, the present invention dissolves the halomethylated high polymer in an organic solvent and then reacts with functional small molecules in a homogeneous phase. During the film formation process, due to the driving force of hydrophobic and hydrophilic phase separation The existence of thiazoles is beneficial to the formation of the penetrating ion channels, thereby improving the electrochemical performance of the prepared anion exchange membrane. A more humane reagent. In addition, due to the resonance structure of the positively charged thiazole functional small molecule side group itself, it has good alkali resistance. In summary, the anion exchange membrane method of the present invention can effectively overcome the above-mentioned shortcomings of preparing anion exchange membranes and can be potentially applied to various fields including alkaline fuel cells.

Detailed ways

The following clearly and completely describes the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

The invention discloses a method for preparing a homogeneous anion exchange membrane. The method comprises the following steps:

Dissolving the halomethylated aromatic polymer in an organic solvent to form a solution to be reacted;

mixing the solution to be reacted with thiazole functional small molecules and performing a nucleophilic substitution reaction to obtain a casting solution of an aromatic polymer with positively charged thiazole functional small molecule side groups; and

The casting solution is coated on a substrate and dried, after which the substrate is removed, or the casting solution is coated on a reinforcing fabric and dried to obtain a homogeneous anion exchange membrane.

The halomethylated aromatic high polymer is halomethylated polyphenylsulfone, polyethersulfone, bisphenol A polysulfone, polyether ether ketone, polyether ketone, polyphenylene ether, polynaphthyl biphenyl Ether sulfone, polynaphthalene polyether sulfone, polynaphthalene polyether sulfone ketone, polyarylether ketone with phenolphthalein side groups, polyarylether sulfone with phenolphthalein side groups, prepared according to known methods from the corresponding Aromatic polymers are obtained by halomethylation, wherein the molar ratio of repeating units containing halomethyl groups to all repeating units is called their degree of halomethylation, taking halomethylated polyethersulfone as an example , its structure is as follows:

The degree of halomethylation of polyethersulfone refers to the molar ratio of repeating units containing chloromethyl groups to all repeating units in polyethersulfone, that is, n in the above structural formula.

The structural formula of the thiazole functional small molecule is as follows:

Wherein R ₁ , R ₂ , and R ₃ are each independently H or an alkyl group.

The organic solvent is toluene, chlorobenzene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone,

During the preparation of the anion exchange membrane, the halomethyl group in the halomethylated polymer undergoes a nucleophilic substitution reaction with the thiazole-like functional small molecule, forming positively charged thiazoles on the main chain of the polymer. Functional small molecular side groups, anion exchange membranes are obtained after coating film heat treatment.

The present invention has no special requirements on the method and order of adding the above-mentioned reaction raw materials, they can be added at the same time or sequentially. The step of forming the casting solution is preferably: dissolving the halomethylated high polymer and thiazole functional small molecules in an organic solvent at the same time, mixing uniformly, and obtaining the casting solution after stirring and reacting, more preferably the halomethylated polymer The base polymer is dissolved in an organic solvent to form a solution to be reacted, and then thiazole functional small molecules are added, mixed evenly, stirred and reacted to obtain a casting solution.

According to the present invention, the mass volume concentration of the solution to be reacted is 1-50m/v (mass/volume)%, preferably 5-20m/v%, more preferably 5-10m/v%. The concentration of the reaction solution is usually controlled within an appropriate range. If the concentration is too high, the concentration of the casting solution will be too high and the film cannot be coated smoothly. If the concentration is too low, the solvent will be wasted.

According to the present invention, the molar ratio between the degree of halomethylation of the high polymer itself and the molar ratio between the halomethyl groups contained in the thiazole functional small molecules and the high polymer is an important factor affecting the properties of the obtained anion exchange membrane, wherein , the halomethylation degree of the polymer is 20%-100mol%, more preferably 40-100mol%, and the molar ratio between the thiazole functional small molecule and the halomethyl group contained in the polymer is 20% -300%, more preferably 80-150%, most preferably 100-150%, it must be pointed out that the high polymer halomethylation degree is too large or too small will affect the mechanical strength, ion conductivity of the anion exchange membrane , water content and ion exchange content and other properties have a significant impact. For the molar ratio between the thiazole functional small molecule and the halomethyl group contained in the polymer, a too low ratio reduces the density of the functional group, considering that the thiazole functional small molecule and the halomethyl group are relatively High reactivity, too high ratio is a waste of functional small molecules.

The halomethylated aromatic polymer used in the present invention is preferably halomethylated polyphenylsulfone, polyethersulfone, bisphenol A polysulfone, polyether ether ketone, polyether ketone, polyphenylene ether, heteronaphthalene Biphenyl polyether sulfone, polynaphthyl biphenyl polyether sulfone, poly naphthalene polyether sulfone ketone, polyarylether ketone with phenolphthalein side group, polyarylether sulfone with phenolphthalein side group.

The thiazole functional small molecule adopted in the present invention is preferably 2-methylthiazole, 2-ethylthiazole, 2-propylthiazole, 2-isopropylthiazole, 4-methylthiazole, 4-ethylthiazole, 4 -Propylthiazole, 4-isopropylthiazole, 5-methylthiazole, 5-ethylthiazole, 5-propylthiazole, 5-isopropylthiazole.

According to the present invention, the reaction temperature between the halomethylated high polymer and the thiazole functional small molecule can be 0-130°C, preferably 25-100°C, more preferably 25-50°C. The reaction time is 4-48h, preferably 8-24h, more preferably 12-24h. Due to the high reactivity between halomethylated polymers and thiazole functional small molecules, the reaction between them can be very rapid under very mild conditions. So too high temperature and too long reaction time are unnecessary.

According to the present invention, after the casting solution is obtained, the casting solution is coated. Wherein, the present invention has no special limitation on the coating method, and a coating method well known to those skilled in the art can be used, preferably salivation. , scrape, spray, dip, flow or spin coating. Specifically, the film coating step adopted in the present invention is preferably: coating the casting solution on a reinforcing fabric, and the reinforcing fabric is preferably polyethylene cloth, polypropylene cloth, nylon cloth, polyester cloth or nylon cloth. Then, heat treatment is carried out after coating the film with the casting solution, the heating temperature is preferably 25-130°C, more preferably 40-100°C, most preferably 50-80°C; the heating time is 4-96 hours , more preferably 10 to 60 hours, most preferably 20 to 48 hours.

The resulting anion exchange membrane of the present invention may be a self-supporting cast membrane layer or may comprise a cast membrane layer and a reinforcing fabric. The aromatic polymer with positively charged thiazole functional small molecular side groups has a cationic part and an anionic part (halide ion), and the cationic part is composed of a halomethylated aromatic polymer main chain and Positively charged thiazole functional small molecular side groups. Taking polyethersulfone with positively charged thiazole functional small molecule side groups as an example, its chemical structural formula is:

Wherein, wherein R ₁ , R ₂ , and R ₃ are H or alkyl, n is the degree of halomethylation of polyethersulfone, and its size is 20-100mol%, and x is the concentration of polyethersulfone in halomethylation. The halomethyl group reacted with thiazole functional small molecules accounts for the molar ratio of all halomethyl groups, and its size is 20-100%

The degree of halomethylation of the polymer is 20-100mol%, preferably 30-100mol%, more preferably 40-100mol%, the thiazole functional small molecule and the halomethyl group contained in the polymer The molar ratio between them is 20-300%, more preferably 30-150%. The water content of the membrane is preferably 2-130%, the ion exchange content is preferably 0.1-3.0mmol.g ^-1 , the mechanical strength of the membrane is preferably 25-58MPa, and the ion conductivity of the membrane is preferably 1-30mS.cm ^-1 .

In summary, the preparation method provided by the present invention has the following characteristics: 1. In the preparation process of the anion exchange membrane, the present invention utilizes an organic solvent to dissolve the halomethylated high polymer and then perform a homogeneous phase with the functional small molecule In the process of film formation, due to the driving force of hydrophobic and hydrophilic phase separation in the membrane, this is conducive to the formation of ion channels through which the electrochemical performance of the membrane can be improved. At the same time, the function of introducing functional groups is small. The amount of molecules added can be greatly reduced, avoiding waste. 2. The present invention can obtain anion exchange membranes with different properties by controlling different conditions in the membrane preparation process, including the ratio between components, reaction temperature and time, Therefore, the corresponding optimal anion exchange membrane can be selected according to the needs of use. 3. The anion exchange membrane prepared by the present invention has the advantages of high ion exchange content, high ion conductivity, uniform and stable structure, high mechanical strength and strong alkali resistance. 5. The membrane preparation method of the present invention is simple and easy, has the potential for series development, and can meet the needs of large-scale application of the prepared membrane in different fields.

In order to further illustrate the technical solution of the present invention, the preferred embodiments of the present invention are described below in conjunction with examples, but it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, rather than limiting the claims of the present invention.

The chemical reagents used in the examples of the present invention are all commercially available.

Example 1

The polyethersulfone (halomethyl 0.75mmol) that 1g halomethylation degree is 18mol% is dissolved in 10ml toluene and forms the solution to be reacted that mass volume concentration is 10m/v%, after adding 0.074g 2-methylthiazole ( 0.75mmol, 1 equivalent), stirred and reacted at 25°C for 24h to obtain a casting solution. The casting solution is cast on a polytetrafluoroethylene plate, heated and dried at 60°C to obtain an anion exchange membrane.

The prepared anion exchange membrane has uniform and transparent appearance, good mechanical strength and high flexibility of the membrane. The related properties tested are: water content 10%, ion exchange capacity 0.65mmolg ^-1 , ion conductance 8mS cm ^-1 , mechanical strength 25MPa.

Example 2

Similar to Example 1, except that the casting solution was scraped on the polyethylene film, heated and dried at 100°C to obtain an anion exchange membrane.

Since the composition of the membrane liquid is the same, the properties of the anion exchange membrane prepared in this example are similar to those in Example 1.

Example 3

Similar to Example 1, except that the casting solution was sprayed on the glass plate, heated and dried at 130° C. to obtain an anion exchange membrane.

Since the composition of the membrane liquid is the same, the properties of the anion exchange membrane prepared in this example are similar to those in Example 1.

Example 4

Similar to Example 1, except that the casting solution was flowed on the aluminum plate, heated and dried at 25° C. to obtain an anion exchange membrane.

Since the composition of the membrane liquid is the same, the properties of the anion exchange membrane prepared in this example are similar to those in Example 1.

Example 5

Similar to Example 1, except that the casting solution was spin-coated on a stainless steel plate, and heated and dried at 130°C to obtain an anion exchange membrane.

Since the composition of the membrane liquid is the same, the properties of the anion exchange membrane prepared in this example are similar to those in Example 1.

Example 6

Similar to Example 1, except that the organic solvent is changed to chlorobenzene, and other conditions remain unchanged, the properties of the anion exchange membrane obtained are similar to those of Example 1.

Example 7

Similar to Example 1, except that the organic solvent was changed to N,N-dimethylformamide, and other conditions remained unchanged, the properties of the anion exchange membrane obtained were similar to those of Example 1.

Example 8

Similar to Example 1, except that the organic solvent was changed to N,N-dimethylacetamide, and other conditions remained unchanged, the properties of the anion exchange membrane obtained were similar to those of Example 1.

Example 9

Similar to Example 1, except that the organic solvent is changed to N-methylpyrrolidone, and other conditions remain unchanged, the properties of the anion exchange membrane obtained are similar to those of Example 1.

As can be seen from comprehensive examples 1-9, the film-forming conditions such as the kind of organic solvent, the mode of coating film and the temperature of baking film do not have too much influence on the properties of the film, so a low-cost, mild-condition forming film is selected. The membrane method is the best choice.

Example 10

Similar to Example 1, except that the reaction time was changed to 4 h, and other conditions remained unchanged, the properties of the obtained anion exchange membrane were similar to those of Example 1.

Example 11

Similar to Example 1, except that the reaction time was changed to 48h, and other conditions remained unchanged, the properties of the obtained anion exchange membrane were similar to those of Example 1.

Comprehensive examples 1, 10, and 11 show that under the high reactivity of thiazole-type functional small molecules and halomethyl groups, the reaction time of thiazole-type functional small molecules and halomethyl groups is close to 100% when the reaction time is 4 hours. It can be preferably 24 h, and prolonging the reaction time has little effect on the membrane properties.

Example 12

Similar to Example 1, except that the amount of 2-methylthiazole added was changed to 0.30 g (2.25 mmol, 3 equivalents), to obtain an anion exchange membrane.

The related properties tested are: water content 16%, ion exchange capacity 0.62mmolg ^-1 , ion conductance 8mS cm ^-1 , mechanical strength 26MPa.

Comprehensive examples 1 and 12 show that under the higher reactivity of thiazole functional small molecules and halomethyl groups, the reaction degree is close to 100% when the molar ratio of thiazole functional small molecules and halomethyl groups is 1:1, and no more The addition of thiazole functional small molecules has little effect on the properties of the membrane.

Example 13

Similar to Example 1, except that the volume of toluene is changed to 2ml, and other conditions remain unchanged, the properties of the anion exchange membrane obtained are similar to those of Example 1.

Example 14

Similar to Example 1, except that the volume of toluene is changed to 100ml, and other conditions remain unchanged, the properties of the anion exchange membrane obtained are similar to those of Example 1.

Example 15

Similar to Example 1, except that the amount of 2-methylthiazole added was changed to 0.038 g (0.38 mmol, 0.5 equivalents), to obtain an anion exchange membrane.

It has a water content of 5%, an ion exchange capacity of 0.3 mmol g ^-1 , an ion conductance of 5 mScm ^-1 , and a mechanical strength of preferably 25 MPa.

Example 16

Similar to Example 1, except that the amount of 2-methylthiazole added was changed to 0.02 g (0.15 mmol, 0.2 equivalents), to obtain an anion exchange membrane.

It has a water content of 2%, an ion exchange capacity of 0.1 mmol g ^-1 , an ion conductance of 1 mScm ^-1 , and a mechanical strength of preferably 24 MPa.

Example 17

1g halomethylation degree is 53% polyethersulfone (halomethyl 2.06mmol) to be dissolved in 10ml toluene and form the solution to be reacted that mass volume concentration is 10%, after adding 0.28ml 2-methylthiazole (3.09mmol , 1.5 equivalents), stirred and reacted at 25°C for 24h to obtain a casting solution. The casting solution is cast on a polytetrafluoroethylene plate, heated and dried at 60°C to obtain an anion exchange membrane.

It has a water content of 50%, an ion exchange capacity of 1.8 mmol g ^-1 , an ion conductance of 20 mScm ^-1 , and a mechanical strength of preferably 41 MPa.

Example 18

1g of polyethersulfone (halomethyl 3.57mmol) with a degree of halomethylation of 100% was dissolved in 10ml of toluene to form a solution to be reacted with a mass volume concentration of 10%, and 0.49ml of 2-methylthiazole (5.36mmol, 1.5 equivalents), stirred and reacted at 25°C for 24h to obtain a casting solution. The casting solution is cast on a polytetrafluoroethylene plate, heated and dried at 60°C to obtain an anion exchange membrane.

It has a water content of 170%, an ion exchange capacity of 3.8 mmol g ^-1 , an ion conductance of 42 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 19

Similar to Example 18, except that the casting solution was scraped on the polyethylene cloth, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 130%, an ion exchange capacity of 2.7 mmol g ^-1 , an ion conductance of 30 mScm ^-1 , and a mechanical strength of preferably 60 MPa.

Example 20

Similar to Example 19, except that the casting solution was scraped on the polypropylene cloth, and other conditions remained unchanged, an anion exchange membrane was obtained. Its properties are similar to those of the anion exchange membrane obtained in Example 17.

Example 21

Similar to Example 19, except that the film casting solution was scraped on the nylon cloth, and other conditions remained unchanged, an anion exchange membrane was obtained. Its properties are similar to those of the anion exchange membrane obtained in Example 17.

Example 22

Similar to Example 19, except that the casting solution was scraped on the polyester cloth, and other conditions remained unchanged, an anion exchange membrane was obtained. Its properties are similar to those of the anion exchange membrane obtained in Example 17.

Example 23

Similar to Example 19, except that the casting solution was scraped on the nylon cloth, and other conditions remained unchanged, an anion exchange membrane was obtained. Its properties are similar to those of the anion exchange membrane obtained in Example 17.

Example 24

Similar to Example 18, except that the halomethylated polyethersulfone was changed to halomethylated polyphenylsulfone, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 160%, an ion exchange capacity of 3.5 mmol g ^-1 , an ion conductance of 34 mScm ^-1 , and a mechanical strength of preferably 50 MPa.

Example 25

Similar to Example 18, except that the halomethylated polyethersulfone was changed to halomethylated bisphenol A polysulfone, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 150%, an ion exchange capacity of 3.2 mmol g ^-1 , an ion conductance of 30 mScm ^-1 , and a mechanical strength of preferably 53 MPa.

Example 26

Similar to Example 18, except that the halomethylated polyethersulfone was changed to halomethylated polyether ether ketone, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 160%, an ion exchange capacity of 3.2 mmol g ^-1 , an ion conductance of 35 mScm ^-1 , and a mechanical strength of preferably 51 MPa.

Example 27

Similar to Example 18, except that the halomethylated polyethersulfone was changed to halomethylated polyetherketone, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 175%, an ion exchange capacity of 3.8 mmol g ^-1 , an ion conductance of 41 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 28

Similar to Example 18, except that the halomethylated polyethersulfone was changed to halomethylated polyphenylene ether, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 180%, an ion exchange capacity of 3.7 mmol g ^-1 , an ion conductance of 40 mScm ^-1 , and a mechanical strength of preferably 51 MPa.

Example 29

Similar to Example 18, except that the halomethylated polyethersulfone was changed to halomethylated polyethersulfone, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 135%, an ion exchange capacity of 2.4 mmol g ^-1 , an ion conductance of 23 mScm ^-1 , and a mechanical strength of preferably 55 MPa.

Example 30

Similar to Example 18, except that the halomethylated polyethersulfone was changed to halomethylated poly(naphthalene biphenyl ether ketone), and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 135%, an ion exchange capacity of 2.5 mmol g ^-1 , an ion conductance of 21 mScm ^-1 , and a mechanical strength of preferably 54 MPa.

Example 31

Similar to Example 18, except that the halomethylated polyethersulfone was changed to halomethylated polyethersulfone ketone, and other conditions remained unchanged, an anion exchange membrane was obtained. Its properties are similar to those of the anion exchange membrane obtained in Example 15.

It has a water content of 125%, an ion exchange capacity of 2.3 mmol g ^-1 , an ion conductance of 20 mScm ^-1 , and a mechanical strength of preferably 55 MPa.

Example 32

Similar to Example 18, except that the halomethylated polyethersulfone is changed to halomethylated polyaryletherketone with phenolphthalein side groups, and other conditions remain unchanged, an anion exchange membrane is obtained. Its properties are similar to those of the anion exchange membrane obtained in Example 15.

It has a water content of 135%, an ion exchange capacity of 2.4 mmol g ^-1 , an ion conductance of 24 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 33

Similar to Example 18, except that the halomethylated polyethersulfone is changed to halomethylated polyarylethersulfone with phenolphthalein side groups, and other conditions remain unchanged, an anion exchange membrane is obtained. Its properties are similar to those of the anion exchange membrane obtained in Example 15.

It has a water content of 130%, an ion exchange capacity of 2.5 mmol g ^-1 , an ion conductance of 26 mScm ^-1 , and a mechanical strength of preferably 50 MPa.

Example 34

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 2-ethylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 160%, an ion exchange capacity of 3.6 mmol g ^-1 , an ion conductance of 39 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 35

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 2-propylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 155%, an ion exchange capacity of 3.4 mmol g ^-1 , an ion conductance of 35 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 36

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 2-isopropylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 150%, an ion exchange capacity of 3.4 mmol g ^-1 , an ion conductance of 31 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 37

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 4-methylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 165%, an ion exchange capacity of 3.8 mmol g ^-1 , an ion conductance of 40 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 38

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 4-ethylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 165%, an ion exchange capacity of 3.6 mmol g ^-1 , an ion conductance of 37 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 39

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 4-propylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 150%, an ion exchange capacity of 3.4 mmol g ^-1 , an ion conductance of 33 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 40

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 4-isopropylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 155%, an ion exchange capacity of 3.4 mmol g ^-1 , an ion conductance of 31 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 41

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 5-methylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 160%, an ion exchange capacity of 3.8 mmol g ^-1 , an ion conductance of 38 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 42

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 5-ethylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 155%, an ion exchange capacity of 3.6 mmol g ^-1 , an ion conductance of 35 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 43

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 5-propylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 145%, an ion exchange capacity of 3.4 mmol g ^-1 , an ion conductance of 31 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 44

Similar to Example 18, except that the thiazole functional small molecule was cast from 2-methylthiazole to 5-isopropylthiazole, and other conditions remained unchanged, an anion exchange membrane was obtained.

It has a water content of 150%, an ion exchange capacity of 3.4 mmol g ^-1 , an ion conductance of 30 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Example 45

Similar to Example 12, except that the reaction temperature is changed from 25° C. to 80° C., and other conditions remain unchanged, the properties of the anion exchange membrane are similar to those of Example 1.

Example 46

Similar to Example 12, except that the reaction temperature is changed from 50° C. to 130° C., and other conditions remain unchanged, the properties of the anion exchange membrane are similar to those of Example 1.

Example 47

Similar to Example 12, except that the reaction temperature is changed from 25°C to 0°C, and other conditions remain unchanged, the properties of the anion exchange membrane are similar to those of Example 1.

Combining Examples 1, 45, 46, and 47, due to the high reactivity between thiazole functional small molecules and halomethyl groups, the reaction can occur rapidly under mild conditions, so the reaction temperature has little effect on the experiment.

In order to investigate the impact of the addition of thiazole functional small molecules and trimethylamine on the properties of the anion exchange membrane, the following will be compared with the comparative example through Example 18:

Example 18

1g of polyethersulfone (halomethyl 3.57mmol) with a degree of halomethylation of 100% was dissolved in 10ml of toluene to form a solution to be reacted with a mass volume concentration of 10%, and 0.49ml of 2-methylthiazole (5.36mmol, 1.5 equivalents), stirred and reacted at 25°C for 24h to obtain a casting solution. The casting solution is cast on a polytetrafluoroethylene plate, heated and dried at 60°C to obtain an anion exchange membrane.

It has a water content of 170%, an ion exchange capacity of 3.8 mmol g ^-1 , an ion conductance of 42 mScm ^-1 , and a mechanical strength of preferably 52 MPa.

Comparative example 1

Dissolve 1g of polyethersulfone (halomethyl 3.57mmol) with a halomethylation degree of 100% in 10ml of toluene to coat a film on a tetrafluoroethylene board, heat and dry at 60°C to form a base film, and then soak the base film In 250ml 33% trimethylamine aqueous solution, react solution 25 ℃ for 5 days, obtain anion exchange membrane.

It has a water content of 120%, an ion exchange capacity of 2.7mmol g ^-1 , an ion conductance of 15mS cm ^-1 ' and a mechanical strength of preferably 44MPa.

Example 18 and Comparative Example 1 used the same halomethylated high polymer to prepare an anion exchange membrane. Because the reaction between trimethylamine and the high polymer in Comparative Example 1 is a heterogeneous reaction, the reaction speed is relatively slow. From the preparation process of the anion-exchange membrane, it can be seen that the preparation process steps of the anion-exchange membrane of Comparative Example 1 are loaded down with trivial details and time-consuming. many. At the same time, compared with Example 18, in Comparative Example 1, all the parameters of the membrane properties have decreased to varying degrees, especially the serious decrease in ion conductance, which is only 35.7% of that of Example 18.

In addition, we also tested the alkali resistance of the anion-exchange membranes in Example 18 and Comparative Example 1 according to the following steps: soak the anion-exchange membrane in 2mol L ^- 1 NaOH aqueous solution at 25°C for 7 days, measure the Changes in the ion exchange capacity of the anion exchange membrane. The results showed that the ion exchange capacity of the anion exchange membrane of Example 18 was 83% of that before soaking in alkaline solution for 7 days, while that of the anion exchange membrane of Example 1 was only 34%.

Based on Example 18 and Comparative Example 1, it can be seen that the method of preparing anion exchange membranes by reacting thiazole functional monomers with halomethylated polymers is more effective than the traditional method of preparing anion exchange membranes by reacting trimethylamine with halomethylated polymers. The anion-exchange membrane method simplifies the steps and shortens the time in the membrane preparation process, and at the same time, the prepared anion-exchange membrane also has different degrees of improvement in various performances than the latter. This proves the superiority of using thiazole functional monomers to prepare anion exchange membranes.

The results of the above examples show that the preparation method of the present invention can effectively control the properties of the prepared anion exchange membrane by controlling various conditions in the membrane preparation process, including the ratio of each component, the temperature and time of reaction, etc. , so as to meet different application requirements; at the same time, through the optimization of conditions, it is convenient to obtain suitable water content, high ion exchange capacity and ion conductivity, and good mechanical strength so that it has the application in alkaline fuel cells. condition.

The above description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the present invention will not be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (17)

1. the preparation method of a homogeneous-phase anion exchange film said method comprising the steps of:

The aromatic high polymer of halomethylation is dissolved in formation question response solution in the organic solvent;

With said question response solution and the little molecular mixing of thiazoles function and carry out nucleophilic substitution, with the casting solution of the aromatic high polymer of the little molecule side group of thiazoles function that obtains having lotus positive electricity; With

Said casting solution is filmed in substrate and drying, afterwards substrate is removed, perhaps said casting solution is filmed on reinforced fabric and drying, thereby obtain homogeneous-phase anion exchange film.

2. preparation method according to claim 1, the aromatic high polymer that it is characterized in that said halomethylation is PPSU, polyether sulfone, bisphenol a polysulfone, polyether-ether-ketone, polyether-ketone, polyphenylene oxide, assorted naphthalene biphenyl polyether sulfone, assorted naphthalene biphenyl polyether sulfone, assorted naphthalene biphenyl polyether sulfone ketone, the PAEK of band phenolphthalein side group or the polyether sulphone of band phenolphthalein side group of halomethylation.

3. preparation method according to claim 1 is characterized in that the little molecule of said thiazoles function has the structure that is expressed from the next:

, R wherein ₁, R ₂, R ₃Be H or alkyl independently of one another.

4. preparation method according to claim 1 is characterized in that said organic solvent is toluene, chlorobenzene, N, dinethylformamide, N, any in N-dimethylacetylamide and the N-methyl pyrrolidone or their mixture.

5. preparation method according to claim 1, the halomethylation degree that it is characterized in that said aromatic high polymer is 20mol%-100mol%.

6. preparation method according to claim 1, the mass and size concentration that it is characterized in that said question response solution is 1-50m/v%.

7. preparation method according to claim 1 is characterized in that halomethyl contained in the aromatic high polymer of said halomethylation and the micromolecular mol ratio of thiazoles function are 1: 0.2-3.

8. preparation method according to claim 1 is characterized in that reaction temperature is 0 ℃ to 130 ℃.

9. preparation method according to claim 1 is characterized in that the reaction time is 1-48h.

10. preparation method according to claim 1 is characterized in that said substrate is polyfluortetraethylene plate, polyethylene film, glass plate, aluminium sheet or corrosion resistant plate.

11. preparation method according to claim 1 is characterized in that said reinforced fabric is polyethylene cloth, polypropylene cloth, polyamide fabric, woven dacron or nylon cloth.

12. preparation method according to claim 1 is characterized in that through curtain coating, knifing, sprinkling, dipping, flows or rotation is filmed.

13. homogeneous-phase anion exchange film; Said homogeneous-phase anion exchange film comprises the casting film layer; Wherein said casting film layer is formed by the aromatic high polymer of the little molecule side group of thiazoles function that has lotus positive electricity, aromatic high polymer that the said aromatic high polymer that has the little molecule side group of thiazoles function of lotus positive electricity is a halomethylation and the micromolecular nucleophilic substitution product of thiazoles function.

14. homogeneous-phase anion exchange film according to claim 13; It is characterized in that the aromatic high polymer of said halomethylation is PPSU, polyether sulfone, bisphenol a polysulfone, polyether-ether-ketone, polyether-ketone, polyphenylene oxide, assorted naphthalene biphenyl polyether sulfone, assorted naphthalene biphenyl polyether sulfone, assorted naphthalene biphenyl polyether sulfone ketone, the PAEK of band phenolphthalein side group or the polyether sulphone of band phenolphthalein side group of halomethylation.

15. homogeneous-phase anion exchange film according to claim 13 is characterized in that, the little molecule side group of the thiazoles function of said lotus positive electricity has the structure that is expressed from the next:

, R wherein ₁, R ₂, R ₃Be H or alkyl independently of one another.

16. homogeneous-phase anion exchange film according to claim 13 is characterized in that, said homogeneous-phase anion exchange film also comprises the reinforced fabric that is positioned at below the said casting film layer.

17. homogeneous-phase anion exchange film according to claim 16 is characterized in that said reinforced fabric is polyethylene cloth, polypropylene cloth, polyamide fabric, woven dacron or nylon cloth.