Terpyridine polymer membrane material with binaphthyl as a skeleton, and preparation method and application thereof

Abstract

The application provides a terguride polymer membrane material with binaphthyl as a skeleton, a preparation method and application thereof, and relates to the fields of polymer materials and gas separation technology. The material is prepared by condensation polymerization of binaphthyl with dimethoxymethane under the catalysis of trifluoroacetic acid, and binaphthyl is used as a diamine monomer. The polymerization reaction has the characteristics of mild reaction condition, high yield and low cost. The obtained terguride polymer is prepared into a gas separation membrane by a solvent evaporation method, and the gas separation membrane has high oxygen permeability and high oxygen / nitrogen selectivity, which exceeds the upper limit of gas separation in 2008. The gas separation membrane material has great development potential.

Description

Technical Field

[0001] This invention relates to the fields of polymer materials and gas separation technology, and in particular to a method for preparing a Teleg base polymer membrane material with binaphthalene as the backbone. Background Technology

[0002] Gas separation technology plays an indispensable role in petrochemicals, energy recovery, and environmental protection. Among these technologies, membrane separation technology, due to its advantages such as low energy consumption, compact equipment, simple operation, and ease of scaling, has gradually replaced traditional thermally driven separation processes and has become a current research hotspot. Statistics show that membrane technology can reduce separation energy consumption by up to 45%, which is of great significance for promoting green energy production and reducing carbon emissions. However, the core bottleneck of this technology lies in the development of high-performance membrane materials. Overcoming the inherent trade-off between permeability and selectivity of polymer membranes, while simultaneously considering the thermal stability, mechanical properties, and processing performance of the materials, is a key issue that urgently needs to be addressed in the industry.

[0003] Self-porous microporous polymers (PIMs), as a novel class of high-performance membrane materials, have effectively solved the problem of insufficient permeability caused by the excessively dense stacking of traditional polymer chains since their formal proposal in 2004, thanks to the inherent microporous structure formed by the rigid twisted structure (porous building blocks) in their molecular backbone. Their BET specific surface area can reach 200~1000 m². 2 With a micropore size concentrated in the range of less than 20 Å, it combines the easy processability of polymers with the high separation performance of inorganic molecular sieves, and has become a core material system for breaking through the Robeson limit. Trogger's base (TB), as a typical porous building block, is widely used to construct ladder polymers (PIMs) due to its unique bridged ring structure and rigidity. These polymers have excellent thermal stability and size sieving ability, and exhibit outstanding performance in the separation of key gases such as H2 / N2, O2 / N2, and CO2 / CH4.

[0004] Bi-naphthalene, an aromatic framework with unique axial chirality and high rigidity, has two naphthalene rings connected by single bonds in its molecular structure, forming a fixed spatial configuration. This not only effectively prevents the close packing of polymer molecular chains, forming inherently uniform micropores, but also allows for flexible control of micropore size and surface chemistry by introducing different substituents, exhibiting high rigidity, good thermal stability, and solubility. Combining the bi-naphthalene framework with the telreg base structure can fully leverage the synergistic advantages of both: bi-naphthalene provides a stable rigid framework and precise microporous structure, while the bridging ring structure of the telreg base further enhances molecular chain rigidity and optimizes gas transport channels, potentially leading to the preparation of novel polymer membrane materials with excellent permeability, selectivity, stability, and processability. Currently, there are no reports on incorporating the bi-naphthalene framework into telreg base polymers for gas separation membrane preparation. The performance defects and application limitations of traditional telreg base polymer membrane materials have driven the development of novel framework-structured telreg base polymers. Therefore, developing a method for preparing a Teleg base polymer membrane material with binaphthalene as the backbone, breaking through the performance bottleneck of existing materials, and meeting the demand for high-performance membrane materials in industrial gas separation has important theoretical research value and practical application prospects. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide a class of inherently microporous polymer membrane materials of the binaphthalene type that are simple to synthesize, cost-effective, and have good gas separation performance.

[0006] To achieve this goal, this invention uses binaphthol as the starting material and prepares it through binaphthol monomers with different locking groups. The obtained polymer material exhibits good gas separation permeability and selectivity, making it suitable for application in the field of gas separation membranes. This type of material has the following structural formula:

[0007]

[0008] Wherein, R is selected from dimethyl, methylene, eth-1,2-ide, propion-1,3-ide, 2-cyclopropylpropion-1,3-ide, and bution-1,4-ide.

[0009] Furthermore, the telage base polymer membrane material with binaphthalene as its backbone provided by the present invention is selected from compounds with the following structures:

[0010]

[0011] A1, A2, A3, A4, and A5 are derived from the diamine monomers in the following structures, respectively.

[0012] .

[0013] This invention also provides a method for preparing the monomer of the above-described telage base polymer membrane material with binaphthalene as the backbone, comprising the following steps:

[0014] The reaction equation is shown below:

[0015]

[0016] Wherein, R is selected from dimethyl, methylene, eth-1,2-ide, propion-1,3-ide, 2-cyclopropylpropion-1,3-ide, and bution-1,4-ide.

[0017] The specific process of the BINOL-I step is as follows:

[0018] Binol (BINOL) was dissolved in DCM. Br2 was slowly added dropwise to the solution over 30 minutes at 0°C. The resulting mixture was stirred at 0°C for 3 hours, during which the solution color gradually changed from deep red to orange. After the reaction was complete, the reaction was quenched with saturated Na2S2O3 solution until the solution turned white. The precipitate was filtered and washed with methyl tert-butyl ether to obtain compound I; the molar ratio of Binol (BINOL) to Br2 was 1:2~10.

[0019] The specific process of steps I-II is as follows:

[0020] (1) Compound I, K2CO3, and CH3I were placed in a double-necked flask under N2 protection, and DMF was added to dissolve them completely. The reaction was then stirred at 50°C for 2 h until the solution changed from yellow to white. After the reaction was completed, the solution was poured into 210 ml of water, and a white solid precipitated out. The solution was filtered to obtain compound II. The molar ratio of compound I to CH3I was 1:4~10.

[0021] (2) Compound I, K2CO3, and NaI were dissolved in DMF. The mixture was stirred at room temperature for 10 minutes, and then dibromomethane was added. The reaction was then stirred at 60°C for 2 hours, and the solution gradually changed from dark yellow to light yellow. After the reaction was completed, the reaction mixture was poured into ice water, and a yellow solid precipitated. The precipitate was collected by filtration, washed with methyl tert-butyl ether, and dried to obtain compound II; the molar ratio of compound I to dibromomethane was 1:3~10.

[0022] (3) Compound I and K2CO3 were dissolved in NMP. The solution was stirred at 80°C. 1,2-Di-p-toluenesulfonyloxyethane was dissolved in NMP and slowly added dropwise to the system. The reaction was stirred overnight, and the solution gradually changed from yellow to white. After the reaction was completed, the solution was poured into ice water, and a white solid precipitated out. The solid was filtered to obtain compound II. The molar ratio of compound I to 1,2-di-p-toluenesulfonyloxyethane was 1:1~10.

[0023] (4) Compound I, K2CO3, and NaI were placed in a single-necked flask. DMF was added and stirred until dissolved. Then 1,3-dibromopropane was added, and the mixture was heated to 60°C and stirred for 4 hours. The color of the solution gradually changed from dark yellow to light yellow. After the reaction was completed, the mixture was poured into ice water, and a white solid precipitated. The precipitate was filtered. The solution was purified by column chromatography (petroleum ether:ethyl acetate = 8:1) to obtain compound II. The molar ratio of compound I to 1,3-dibromopropane was 1:3~10.

[0024] (5) Compound I, K2CO3, and NaI were placed in a single-necked flask. DMF was added and stirred until dissolved. Then 1,1-bis(bromomethyl)cyclopropane was added, and the mixture was heated to 60°C and stirred for 4 hours. The color of the solution gradually changed from dark yellow to light yellow. After the reaction was completed, the mixture was poured into ice water, and a yellow solid precipitated. The precipitate was filtered. The precipitate was washed with methyl tert-butyl ether to obtain compound II. The molar ratio of compound I to 1,1-bis(bromomethyl)cyclopropane was 1:3~10.

[0025] The specific process of steps II-III is as follows:

[0026] The synthesis of compound III followed the same procedure for five different locked compounds II. Compound II, sodium tert-butoxide, Pd2(dba)3, and BINAP were placed in a double-necked flask under a nitrogen atmosphere. Toluene was added, and the mixture was stirred for 10 minutes until completely dissolved. Then, benzophenone imine was added, and the mixture was heated under reflux with stirring for 18 hours, during which the solution changed from orange-yellow to gray-black. After the reaction was complete, the mixture was extracted three times with ethyl acetate and water. The organic phases were combined, dried, and rotary evaporated. Subsequently, 20 ml of THF and 30 ml of 1 mol / L hydrochloric acid were added, and the mixture was heated under reflux with stirring for 6 hours. The solution color gradually changed from deep yellow to light yellow. After the reaction was complete, the mixture was extracted three times with DCM and water. The aqueous phase was collected, and 1 mol / L NaOH solution was added dropwise until the system became alkaline, precipitating a white solid. The precipitate was collected by filtration to obtain compound III, namely the self-locked diamine monomers A1-A5; the molar ratio of compound II to benzophenone imine was 1:3-10.

[0027] The monomers A1~A5 described in this invention are polymerized with dimethoxymethane to generate compounds TB-A1~A5.

[0028] The reaction equation is shown below:

[0029]

[0030] The specific steps are as follows:

[0031] The process involves polymerizing intramolecularly cyclized diamine monomers (A1-A5 molecules) with dimethoxymethane, including the following steps:

[0032] The locked diamine monomers A1~A5 were placed in reaction vessels, and solvent and dimethoxymethane were added. The mixture was stirred until the raw materials were completely dissolved. Then, the ice-water bath was removed, and the temperature was gradually raised to room temperature while stirring continuously until the reaction solution became viscous. The reaction solution was poured into ammonia water to precipitate the polymer. The polymer was washed repeatedly with water and acetone and dried. Finally, the polymer was dissolved in chloroform and reprecipitated twice with methanol. The polymer was then dried in an 80 °C oven to obtain polymers TB-A1~A5. The molar ratio of A1~A5 to dimethoxymethane was 1:5~10.

[0033] The present invention further provides the application of the above-described telage base polymer membrane material with binaphthalene as the backbone in gas separation membranes.

[0034] Based on the applications described above, the telage base polymer membrane material with naphthalene as its backbone of the present invention can be used as a gas separation membrane. The preparation method of the gas separation membrane in the above applications involves the following steps:

[0035] The Teleg base polymer was dissolved in chloroform with a solid content of 3 wt%, filtered through a PTFE filter with a diameter of 0.22 µm into a petri dish with a radius of 2.5 cm, and then the solvent was allowed to evaporate within 2 days to obtain a gas separation membrane with an average thickness of approximately 60 µm.

[0036] The beneficial effects of this invention are as follows:

[0037] 1. The present invention provides a Teleg base polymer membrane material with binaphthalene as the backbone, which has good oxygen permeability and oxygen / nitrogen selectivity.

[0038] 2. This invention provides a Teleg base polymer membrane material with binaphthalene as the backbone. Binaphthalene provides a stable rigid backbone and a precise microporous structure, while the bridged ring structure of the Teleg base further enhances the rigidity of the molecular chain and optimizes the gas transport channels. The combination of these two elements improves the gas separation performance of the polymer material.

[0039] 3. Based on the length and steric hindrance effect of intramolecular cyclization bridging groups, bridging groups such as dimethyl, methylene, eth-1,2-idexyl, prop-1,3-idexyl, 2-cyclopropylprop-1,3-idexyl, and but-1,4-idexyl are introduced between the hydroxyl groups of the naphthalene rings. This effectively restricts the conformational flexibility of the two naphthalene rings around the C-C bond, improves the overall rigidity of the polymer, and allows for the adjustment of the degree of torsion by controlling the length of the bridging groups, thereby achieving controllable adjustment of the membrane material's selectivity and permeability coefficient.

[0040] 4. The present invention provides an application of a telage base polymer membrane material with binaphthalene as the backbone in gas separation membranes. The prepared TB-A3 exhibits the best gas separation performance, with an O2 permeability of 389.71 Barrer and an O2 / N2 selectivity of 4.87, exceeding the 2008 Robeson upper limit. Compared with the non-intramolecularly cyclized TB-A1, the O2 permeability of TB-A1 is only 32% of that of TB-A3. Attached Figure Description

[0041] Figure 1 The NMR spectrum of formula TB-A1 prepared according to the present invention;

[0042] Figure 2 The NMR spectrum of formula TB-A3 prepared according to the present invention;

[0043] Figure 3 A comparison of CO2 / CH4 ratio and Robeson's upper limit in the gas separation performance of TB-A1, TB-A3, TB-A4, and TB-A5 membrane materials prepared in this invention;

[0044] Figure 4 A comparison of O2 / N2 and Robeson's upper limit in the gas separation performance of TB-A1, TB-A3, TB-A4, and TB-A5 membrane materials prepared in this invention; Detailed Implementation

[0045] The present invention will be described in detail below with reference to embodiments, so as to provide a clearer understanding of the present invention.

[0046] This invention provides a class of Teleg base polymer membrane materials with binaphthalene as the backbone, the general structural formula of which is shown below:

[0047]

[0048] Wherein, R is selected from dimethyl, methylene, eth-1,2-ide, propion-1,3-ide, 2-cyclopropylpropion-1,3-ide, and bution-1,4-ide.

[0049] Specifically, this type of material is one of the following compounds with the structures TB-A1, TB-A2, TB-A3, TB-A4, and TB-A5:

[0050]

[0051] Example 1: Synthesis of polymer TB-A1

[0052]

[0053] Synthesis of Compound 1:

[0054] BINOL (1 g, 3.49 mmol) was dissolved in DCM (20 ml). Br2 (0.4 ml, 7.69 mmol) was slowly added dropwise to this solution over 30 minutes at 0 °C. The resulting mixture was stirred at 0 °C for 3 hours, and the solution color gradually changed from dark red to orange. After the reaction was complete, the reaction was quenched with saturated Na2S2O3 solution until the solution turned white. The precipitate was filtered and washed with methyl tert-butyl ether to give a white powdery product 1 (1.2 g, 78%).

[0055] 1 H NMR (400 MHz, DMSO-d6) δ 9.52 (s, 2H), 8.12 (d, J = 2.1 Hz, 2H), 7.87 (d, J = 8.9 Hz, 2H), 7.45–7.26 (m, 4H), 6.85 (d, J = 9.0 Hz, 2H).

[0056] Synthesis of compound 2:

[0057] Compound 1 (2 g, 4.5 mmol), K₂CO₃ (5 g, 36 mmol), and CH₃I (1.68 ml, 27 mmol) were placed in a N₂-protected double-necked flask, and DMF (30 ml) was added to dissolve them completely. The mixture was then stirred at 50 °C for 2 h until the reaction was complete, at which point the solution changed from yellow to white. After the reaction was complete, the solution was poured into 210 ml of water, and a white solid precipitated out. The precipitate was filtered to obtain a white solid product 2 (1.5 g, 70%).

[0058] 1 H NMR (400 MHz, Chloroform-d) δ 8.02 (d, J = 2.1 Hz, 2H), 7.89 (d, J= 9.0 Hz, 2H), 7.46 (d, J = 9.1 Hz, 2H), 7.26 (s, 2H), 6.93 (d, J = 9.1 Hz,2H), 3.76 (s, 6H).

[0059] Synthesis of A1 monomer:

[0060] Compound 2 (1 g, 2.11 mmol), sodium tert-butoxide (968 mg, 10.08 mmol), Pd2(dba)3 (60 mg, 0.06 mmol), and BINAP (41 mg, 0.06 mmol) were placed in a two-necked flask under a nitrogen atmosphere. Toluene (15 mL) and benzophenone imine (1.06 mL, 6.33 mmol) were then added. The mixture was stirred under reflux for 18 h, during which the solution changed from orange to grayish-black. After the reaction was complete, the mixture was extracted three times with ethyl acetate and water. The combined organic phases were dried and rotary evaporated. The solution was then dissolved in 20 mL of THF, and 40 mL of 1 mol / L HCl was added. The mixture was stirred under reflux for 6 h, during which the solution gradually changed from orange to pale yellow. After the reaction was complete, the mixture was extracted three times with DCM and water. The aqueous phase was collected, and 1 mol / L NaOH solution was added dropwise until the system became alkaline, resulting in the precipitation of a white solid in the aqueous phase. The precipitate was filtered to give a white solid A1 (489 mg, 67%).

[0061] Synthesis of TB-A1 polymer:

[0062] Add A1 (250 mg, 0.727 mmol) to a 50 ml double-necked flask under N2 protection. Add dimethoxymethane (0.32 ml, 3.63 mmol) and TFA (1.67 ml, 21.8 mmol) under an ice-water bath. After stirring for 10 min, remove the ice-water bath and stir at room temperature for 1.5 h. The solution becomes viscous. Slowly pour the solution into vigorously stirred ammonia water. A large amount of white fumes are generated, and a white flocculent solid precipitate forms. Filter and collect the precipitate. Wash the precipitate twice with water and acetone. Finally, dissolve the solid in chloroform and precipitate again twice with methanol. Dry in an 80 °C oven to obtain the Tereg base polymer TB-A1 (280 mg, 87%). The NMR spectrum of TB-A1 prepared in this example is shown below. Figure 1 As shown.

[0063] Example 2: Synthesis of polymer TB-A2

[0064]

[0065] Synthesis of compound 3:

[0066] Compound 1 (1 g, 2.25 mmol), K₂CO₃ (1.86 g, 13.5 mmol), and NaI (24 mg, 0.155 mmol) were dissolved in DMF (14 ml). The mixture was stirred at room temperature for 10 minutes, and then dibromomethane (0.5 ml, 6.75 mmol) was added. The reaction mixture was then stirred at 60 °C for 2 hours, during which the solution gradually changed from deep yellow to light yellow. After the reaction was complete, the reaction mixture was poured into ice water (200 ml), and a yellow solid precipitated. The precipitate was collected by filtration, washed with methyl tert-butyl ether, and dried to give product 3 (810 mg, 78%) as a white powder.

[0067] 1 H NMR (400 MHz, Chloroform-d) δ 8.10 (d, J = 2.0 Hz, 2H), 7.89 (d, J= 8.7 Hz, 2H), 7.50 (d, J = 8.8 Hz, 2H), 7.38 (dd, J = 9.1, 2.1 Hz, 2H), 7.31(d, J = 9.1 Hz, 2H), 5.69 (s, 2H).

[0068] Synthesis of A2 monomer:

[0069] Compound 3 (1 g, 2.19 mmol), sodium tert-butoxide (1 g, 10.42 mmol), Pd2(dba)3 (60 mg, 0.066 mmol), and BINAP (41 mg, 0.066 mmol) were placed in a two-necked flask under a nitrogen atmosphere. Toluene (12 ml) was added, and the mixture was stirred for 10 minutes until completely dissolved. Then, benzophenone imine (1.1 ml, 6.57 mmol) was added, and the mixture was stirred under reflux for 18 hours, during which the solution changed from orange to grayish-black. After the reaction was complete, the mixture was extracted three times with ethyl acetate and water. The organic phases were combined, dried, and rotary evaporated. Subsequently, 20 ml of THF and 30 ml of 1 mol / L hydrochloric acid were added, and the mixture was stirred under reflux for 6 hours. The solution color gradually changed from deep yellow to light yellow. After the reaction was complete, the mixture was extracted three times with DCM and water. The aqueous phase was collected, and 1 mol / L NaOH solution was added dropwise until the system became alkaline, precipitating a yellow solid. The precipitate was collected by filtration to obtain a yellow solid A2 (401 mg, 56%).

[0070] 1H NMR (400 MHz, DMSO-d6) δ 7.65 (d, J = 8.7 Hz, 2H), 7.28 (d, J =8.7 Hz, 2H), 7.10 (d, J = 9.0 Hz, 2H), 6.93 (d, J = 2.3 Hz, 2H), 6.79 (dd, J= 9.0, 2.3 Hz, 2H), 5.52 (s, 2H), 5.37 (s, 4H).

[0071] Synthesis of TB-A2 polymer:

[0072] A2 (250 mg, 0.762 mmol) and anhydrous DCM (1 ml, 15.6 mmol) were added to a 50 ml double-necked flask under N2 protection. Dimethoxymethane (0.33 ml, 3.81 mmol) and TFA (1 ml, 13.08 mmol) were added under an ice-water bath. After stirring for 10 min, TFA (1 ml, 13.08 mmol) was slowly added dropwise. The ice-water bath was removed, and the mixture was stirred at room temperature for 1 h. The solution became gel-like. It was slowly poured into a vigorously stirred ammonia solution, which produced a large amount of white fumes and a white flocculent solid precipitate. The precipitate was collected by filtration and washed twice with water and acetone. Finally, the solid was dissolved in chloroform and reprecipitated twice with methanol. The solution was dried in an 80 ℃ oven to obtain the Teleg base polymer TB-A2 (271 mg, 87%).

[0073] Example 3: Synthesis of polymer TB-A3

[0074]

[0075] Synthesis of compound 4:

[0076] Compound 1 (500 mg, 1.126 mmol) and K₂CO₃ (186 mg, 1.35 mmol) were dissolved in NMP (3 ml). The solution was stirred at 80 °C. 1,2-Ditoluenesulfonyloxyethane (416 mg, 1.126 mmol) was dissolved in NMP (2 ml) and slowly added dropwise to the system while stirring overnight. The solution gradually changed from yellow to white. After the reaction was complete, the solution was poured into 200 ml of ice water, and a white solid precipitated. The precipitate was filtered to give a white solid product 4 (280 mg, 56%).

[0077] 1H NMR (400 MHz, Chloroform-d) δ 8.06 (d, J = 2.0 Hz, 2H), 7.89 (d, J= 8.9 Hz, 2H), 7.46 (d, J = 8.8 Hz, 2H), 7.31 (dd, J = 9.1, 2.1 Hz, 2H), 7.07(d, J = 9.0 Hz, 2H), 4.42 (d, J = 9.0 Hz, 2H), 4.16 (d, J = 8.9 Hz, 2H).

[0078] Synthesis of A3 monomer:

[0079] Compound 4 (1 g, 2.13 mmol), sodium tert-butoxide (970 mg, 10.11 mmol), Pd2(dba)3 (58 mg, 0.064 mmol), and BINAP (40 mg, 0.064 mmol) were placed in a two-necked flask under a nitrogen atmosphere. Toluene (12 mL) was added, and the mixture was stirred for 10 minutes until completely dissolved. Then, benzophenone imine (1 mL, 6.39 mmol) was added, and the mixture was stirred under reflux for 18 hours, during which the solution changed from orange to dark red. After the reaction was complete, the mixture was extracted three times with ethyl acetate and water. The organic phases were combined, dried, and rotary evaporated. Subsequently, 20 mL of THF and 30 mL of 1 mol / L hydrochloric acid were added, and the mixture was stirred under reflux for 6 hours. The solution color gradually changed from deep yellow to light yellow. After the reaction was complete, the mixture was extracted three times with DCM and water. The aqueous phase was collected, and 1 mol / L NaOH solution was added dropwise until the system became alkaline, precipitating a yellow solid. The precipitate was collected by filtration to obtain a yellow solid A3 (431 mg, 59%).

[0080] 1 H NMR (400 MHz, Chloroform-d) δ 7.67 (d, J = 8.8 Hz, 2H), 7.32 (d, J= 8.8 Hz, 2H), 7.07 (d, J = 9.0 Hz, 2H), 6.97 (d, J = 2.4 Hz, 2H), 6.62 (dd,J = 9.0, 2.4 Hz, 2H), 4.34 (d, J = 8.9 Hz, 2H), 4.12 (d, J = 9.0 Hz, 2H), 3.89 – 3.55 (m, 4H).

[0081] Synthesis of TB-A3 polymer:

[0082] A3 (250 mg, 0.731 mmol) and anhydrous DCM (1 ml, 15.6 mmol) were added to a 50 ml double-necked flask under N2 protection. Dimethoxymethane (0.32 ml, 3.65 mmol) and TFA (1 ml, 13.08 mmol) were added under an ice-water bath. After stirring for 10 min, TFA (1 ml, 13.08 mmol) was slowly added dropwise. The ice-water bath was removed, and the mixture was stirred at room temperature for 1.5 h. The solution became gel-like. This gel was slowly poured into vigorously stirred ammonia water, resulting in the formation of a large amount of white fumes and the precipitation of a white flocculent solid. The precipitate was collected by filtration and washed twice with water and acetone. Finally, the solid was dissolved in chloroform and reprecipitated twice with methanol. The solid was then dried in an oven at 80 °C to obtain the Teleg base polymer TB-A3 (269 mg, 87%). The NMR spectrum of TB-A3 prepared in this example is shown below. Figure 2 As shown.

[0083] Example 4: Synthesis of polymer TB-A4

[0084]

[0085] Synthesis of compound 5:

[0086] Compound 1 (500 mg, 1.126 mmol), K₂CO₃ (932 mg, 6.765 mmol), and NaI (12 mg, 0.08 mmol) were placed in a single-necked flask. DMF (5 ml) was added and stirred until dissolved. Then 1,3-dibromopropane (0.35 ml, 3.38 mmol) was added, and the mixture was heated to 60 °C and stirred for 4 hours. The solution color gradually changed from dark yellow to light yellow. After the reaction was complete, the solution was poured into 100 ml of ice water, and a white solid precipitated. The precipitate was filtered and purified by column chromatography (petroleum ether:ethyl acetate = 8:1) to give white solid 5 (360 mg, 66%).

[0087] 1 H NMR (400 MHz, Chloroform-d) δ 8.05 (d, J = 2.0 Hz, 2H), 7.87 (d, J= 8.9 Hz, 2H), 7.47 (d, J = 8.9 Hz, 2H), 7.32 (dd, J = 9.0, 2.1 Hz, 2H), 7.09(d, J = 9.0 Hz, 2H), 4.44 – 4.28 (m, 4H), 1.95 (p, J = 5.3 Hz, 2H).

[0088] Synthesis of A4 monomer:

[0089] Compound 5 (1 g, 2.06 mmol), sodium tert-butoxide (942 mg, 9.81 mmol), Pd2(dba)3 (57 mg, 0.062 mmol), and BINAP (38 mg, 0.062 mmol) were placed in a two-necked flask under a nitrogen atmosphere. Toluene (10 ml) was added, and the mixture was stirred for 10 minutes until completely dissolved. Then, benzophenone imine (0.9 ml, 6.18 mmol) was added, and the mixture was stirred under reflux for 18 hours, during which the solution changed from orange-yellow to dark red. After the reaction was complete, the mixture was extracted three times with ethyl acetate and water. The organic phases were combined, dried, and rotary evaporated. Subsequently, 20 ml of THF and 30 ml of 1 mol / L hydrochloric acid were added, and the mixture was stirred under reflux for 6 hours. The solution color gradually changed from deep yellow to light yellow. After the reaction was complete, the mixture was extracted three times with DCM and water. The aqueous phase was collected, and 1 mol / L NaOH solution was added dropwise until the system became alkaline, precipitating a yellow solid. The precipitate was collected by filtration to obtain a yellow solid A4 (451 mg, 61%).

[0090] 1 H NMR (400 MHz, DMSO-d6) δ 7.59 (d, J = 8.9 Hz, 2H), 7.32 (d, J =8.9 Hz, 2H), 6.89 (d, J = 2.2 Hz, 2H), 6.80 (d, J = 8.9 Hz, 2H), 6.71 (dd, J= 9.0, 2.3 Hz, 2H), 5.18 (s, 4H), 4.17 (qd, J = 11.8, 6.6 Hz, 4H), 1.77 (t, J= 5.1 Hz, 2H).

[0091] Synthesis of TB-A4 polymer:

[0092] Add A4 (250 mg, 0.704 mmol) and anhydrous DCM (1 ml, 15.6 mmol) to a 50 ml double-necked flask under N2 protection. Add dimethoxymethane (0.31 ml, 3.52 mmol) and TFA (1 ml, 13.08 mmol) under an ice-water bath. Stir for 10 min, then slowly add TFA (1 ml, 13.08 mmol). Remove the ice-water bath and stir at room temperature for 45 min. The solution becomes gel-like. Slowly pour it into vigorously stirred ammonia water. A large amount of white fumes are generated, and a white flocculent solid precipitate is formed. Filter and collect the precipitate. Wash it twice with water and acetone. Finally, dissolve the solid in chloroform and precipitate it again twice with methanol. Dry it in an 80 ℃ oven to obtain the Teleg base polymer TB-A4 (266 mg, 83%).

[0093] Example 5: Synthesis of polymer TB-A5

[0094]

[0095] Synthesis of compound 6:

[0096] Compound 1 (1 g, 2.25 mmol), K₂CO₃ (1.8 g, 13.52 mmol), and NaI (23 mg, 0.15 mmol) were placed in a single-necked flask. DMF (10 ml) was added and stirred until dissolved. Then 1,1-bis(bromomethyl)cyclopropane (0.8 ml, 6.77 mmol) was added, and the mixture was heated to 60 °C and stirred for 4 hours. The solution color gradually changed from deep yellow to light yellow. After the reaction was complete, the solution was poured into 200 ml of ice water, and a yellow solid precipitated. The precipitate was filtered and washed with methyl tert-butyl ether to give yellow solid 6 (750 mg, 65%).

[0097] 1 H NMR (400 MHz, Chloroform-d) δ 8.05 (d, J = 2.0 Hz, 2H), 7.85 (d, J= 8.8 Hz, 2H), 7.43 (d, J = 8.9 Hz, 2H), 7.31 (dd, J = 9.0, 2.0 Hz, 2H), 7.06(d, J = 9.0 Hz, 2H), 4.20 (d, J = 12.2 Hz, 2H), 4.07 (d, J = 12.2 Hz, 2H), 0.61 – 0.34 (m, 4H).

[0098] Synthesis of A5 monomer:

[0099] Compound 6 (1 g, 1.96 mmol), sodium tert-butoxide (894 mg, 9.31 mmol), Pd2(dba)3 (54 mg, 0.059 mmol), and BINAP (36 mg, 0.059 mmol) were placed in a two-necked flask under a nitrogen atmosphere. Toluene (10 ml) was added, and the mixture was stirred for 10 minutes until completely dissolved. Then, benzophenone imine (0.9 ml, 5.88 mmol) was added, and the mixture was stirred under reflux for 18 hours, during which the solution changed from orange-yellow to gray-black. After the reaction was complete, the mixture was extracted three times with ethyl acetate and water. The organic phases were combined, dried, and rotary evaporated. Subsequently, 20 ml of THF and 30 ml of 1 mol / L hydrochloric acid were added, and the mixture was stirred under reflux for 6 hours. The solution color gradually changed from deep yellow to light yellow. After the reaction was complete, the mixture was extracted three times with DCM and water. The aqueous phase was collected, and 1 mol / L NaOH solution was added dropwise until the system became alkaline, precipitating a white solid. The precipitate was collected by filtration to give a white solid A5 (441 mg, 59%).

[0100] 1 H NMR (400 MHz, DMSO-d6) δ 7.56 (d, J = 8.8 Hz, 2H), 7.30 (d, J =8.9 Hz, 2H), 6.88 (d, J = 2.2 Hz, 2H), 6.78 (d, J = 9.0 Hz, 2H), 6.70 (dd, J= 9.0, 2.3 Hz, 2H), 5.18 (s, 4H), 4.08 (d, J = 12.3 Hz, 2H), 3.92 (d, J =12.2 Hz, 2H), 0.36 (d, J = 3.0 Hz, 4H).

[0101] Synthesis of TB-A5 polymer:

[0102] Add A5 (250 mg, 0.654 mmol) and anhydrous DCM (1 ml, 15.6 mmol) to a 50 ml double-necked flask under N2 protection. Add dimethoxymethane (0.29 ml, 3.27 mmol) and TFA (1 ml, 13.08 mmol) under an ice-water bath. Stir for 10 min, then slowly add TFA (1 ml, 13.08 mmol). Remove the ice-water bath and stir at room temperature for 45 min. The solution becomes gel-like. Slowly pour it into vigorously stirred ammonia water. A large amount of white smoke is generated, and a white flocculent solid precipitate is formed. Filter and collect the precipitate. Wash it twice with water and acetone. Finally, dissolve the solid in chloroform and precipitate it again twice with methanol. Dry it in an 80 ℃ oven to obtain the Teleg base polymer TB-A5 (263 mg, 84%).

[0103] Application Example 1:

[0104] The pure gas permeability of the prepared TB membrane was tested using the time-delay method at 35 °C and 2 bar. The gas testing sequence was CH4, N2, O2, and CO2. During the gas testing, the downstream test valve was opened, and a vacuum pump was used to evacuate for 4-6 hours. Then, the upstream valve was opened, and a vacuum pump was used to evacuate for 0.5-1 hours before the gas was introduced and the test began. Table 1 shows the pure gas permeability and ideal selectivity data of the TB membrane. Figure 3 and Figure 4 It can be seen that the O2 / N2 separation performance of all TB membranes is better than that of CO2 / CH4 separation performance; among the TB-A3 Teleg base membranes prepared from the ethyl-1,2-ide-locked monomer A3, the O2 / N2 separation performance is as follows: Figure 4 As shown, it surpasses the Robeson gas separation limit set in 2008.

[0105] The Teleg alkaline membrane exhibits superior O2 / N2 separation performance compared to CO2 / CH4, primarily due to its molecular sieving properties. This superiority stems from its rigid V-shaped double-bridged ring structure, which creates a narrow distribution of submicropores (3.4–3.7 Å). These pores closely match the kinetic diameter windows of O2 and N2 (3.46 Å and 3.64 Å, respectively). Furthermore, both O2 and N2 are nonpolar, low-condensability gases with minimal difference in solubility coefficients within the membrane. Therefore, the interference of solubility selectivity on overall separation is negligible, and the separation performance is entirely determined by diffusion selectivity dominated by molecular sieving, maximizing the sieving effect. In contrast, CO2 and CH4 have significantly different kinetic diameters (3.3 Å and 3.8 Å, respectively). The pore size of CO2 is poorly matched with the lower limit of the pore size, and it cannot be preferentially and rapidly transferred through size sieving. CH4 is only slightly higher than the upper limit of the pore size and cannot be completely retained. Moreover, the difference in molecular configuration between the two further weakens the size sieving effect. At the same time, the strong interaction between CO2 and the tertiary amine N atoms in the membrane will also cause swelling and plasticization, and adsorption hindrance effect, which will destroy the narrow pore size distribution of the membrane and offset the diffusion selectivity advantage. Ultimately, its molecular sieving-dominated separation performance is far inferior to that of the O2 / N2 system.

[0106] Table 1 Pure Gas Separation Performance of Teleg Alkali Membrane Materials

[0107]

[0108] a .1 Barrer = 10 -10 (cm 3 (STP)·cm) / (cm 2 ·sec cmHg).

Claims

1. A Teleg base polymer membrane material with binaphthalene as its backbone, characterized in that, The general structural formula is as follows: Wherein, R is selected from dimethyl, methylene, eth-1,2-ide, propion-1,3-ide, 2-cyclopropylpropion-1,3-ide, and bution-1,4-ide.

2. The Teleg base polymer membrane material with binaphthalene as the backbone according to claim 1, characterized in that, The material is one of the following compounds with the structures TB-A1, TB-A2, TB-A3, TB-A4, and TB-A5: A1, A2, A3, A4, and A5 are derived from the diamine monomers in the following structures, respectively. 。 3. The method for preparing the binaphthalene-teleg base polymer gas separation membrane material according to claim 2, characterized in that, Includes the following steps: The locked diamine monomers A1~A5 were placed in separate reaction vessels, and solvent and dimethoxymethane were added. The mixture was stirred until the raw materials were completely dissolved. Then, the ice-water bath was removed, and the temperature was gradually raised to room temperature while stirring continuously until the reaction solution became viscous. The reaction solution was poured into ammonia water to precipitate the polymer. The polymer was washed repeatedly with water and acetone and dried. Finally, the polymer was dissolved in chloroform and reprecipitated twice with methanol. The polymer was then dried in an oven at 80 °C to obtain polymers TB-A1~A5. The molar ratio of A1~A5 to dimethoxymethane was 1:5~10. The reaction equation is shown below: Wherein, R is selected from dimethyl, methylene, eth-1,2-ide, propion-1,3-ide, 2-cyclopropylpropion-1,3-ide, and bution-1,4-ide.

4. The method for preparing the binaphthalene-teleg base polymer gas separation membrane material according to claim 3, characterized in that, Using dichloromethane and trifluoroacetic acid as solvents, or without adding dichloromethane but using only trifluoroacetic acid as solvent.

5. The method for preparing the binaphthalene-teleg base polymer gas separation membrane material according to claim 3, characterized in that, The monomers A1 to A5 are obtained through the following method: (a) BINOL is brominated with bromine water to generate intermediate I; (b) Compound I undergoes a cyclization reaction with iodomethane / dimethyl sulfate / dibromomethane / dibromoethane / 1,2-di-p-toluenesulfonyloxyethane / 1,3-dibromopropane / 1,1-bis(bromomethyl)cyclopropane to generate intermediate II; (c) To make compound II undergo palladium-catalyzed coupling and hydrolysis to produce target product III, namely the intramolecularly cyclized locked diamine monomers A1~A5; The reaction equation is shown below: Wherein, R is selected from dimethyl, methylene, eth-1,2-ide, propion-1,3-ide, 2-cyclopropylpropion-1,3-ide, and bution-1,4-ide.

6. The application of the Teleg base polymer membrane material with binaphthalene as the backbone as described in claim 1 or 2 in gas separation membranes.

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