Synthesis method of sequence-encodable polyionic liquid
The copper-catalyzed synthesis of sequence-encoded ionic liquids addresses the complexity and low yield issues of existing methods, providing clear molecular structures and high data storage capacity for biomedicine and electrochemistry applications.
Patent Information
- Application Number
- CN202211718879.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-12-30
- Publication Date
- 2025-07-15
- Estimated Expiration
- 2042-12-30
AI Technical Summary
The prior art has problems such as cumbersome reaction steps, complex purification work, low yield and lack of effective decoding methods when synthesizing sequence monodisperse polymers.
The azide-alkyne click reaction catalyzed with copper catalyzed and the quaternization reaction were performed alternately. The sequence monodispersed polyion liquid was prepared by the stepwise growth method, and a series of reactions were performed with thiol-tertiary amine compounds and bromoal alcohol, sulfoxide chloride, sodium azide, bromopropyne and other compounds were carried out, combining inert gas protection and post-treatment methods.
A sequence single-dispersed polyion liquid with a single molecular weight distribution and a clear and encodeable structure was successfully prepared. The reaction conditions were simple, the purification method was simple, the yield and yield were high. The polymer structure decoding was achieved through mass spectrometry detection, and it had multiple encoding possibilities.
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Figure CN116041266B_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of materials, and particularly relates to a method for synthesizing sequence-encodable polyionic liquids. Background Art
[0002] Polyionic liquids are a class of polymers containing a large number of ionic bonds and anionic and cationic groups in their structures. They simultaneously possess the characteristics and properties of ionic compounds and high-molecular polymers, and are becoming a new type of material with a wide range of application scenarios. The synthesis of polyionic liquids generally involves free radical polymerization of monomers containing ionic groups, or functionalization of non-ionic polymers to introduce ionic bonds to achieve the synthesis of polyionic liquids. Currently, polyionic liquids have a wide range of applications in the fields of electrochemistry, energy science, materials science, etc.
[0003] Sequence monodisperse polymers are a class of polymers with uniform molecular weights, and their polydispersity is strictly 1, and each molecule has the same molecular weight. The precisely controlled structure endows them with a series of special physical, chemical, and biological properties, making them a highly potential polymer material in many aspects. The synthesis methods of sequence polymers mainly include stepwise polymerization, exponential growth method, monomer insertion method, etc. Generally, there are problems such as cumbersome reaction steps, complex purification work, low yield and productivity. At the same time, sequence polymers can be "encoded" by monomer selection to control their structures, but generally there is no suitable characterization method to achieve "decoding" to read their structures. Therefore, it is of great significance to develop a method for synthesizing sequence monodisperse polymers with high yield and productivity, simple reaction steps, and mild conditions, which can ensure the information carrying capacity and density through monomer design, and achieve reverse decoding through simple characterization. Summary of the Invention
[0004] The purpose of the present invention is to provide a method for synthesizing sequence-encodable polyionic liquids, and the prepared sequence monodisperse polymers have the advantages of simple reaction conditions, high yield and productivity, etc.
[0005] The above technical purpose of the present invention is achieved through the following technical solutions:
[0006] A method for synthesizing sequence-encodable polyionic liquids includes the following steps:
[0007] S1:
[0008]
[0009] Mix the mercapto-tertiary amine compound with a sodium hydroxide solution having a concentration of 2 - 6 mol / L. The molar ratio of the mercapto-tertiary amine compound to sodium hydroxide is 1:2 - 3. Add bromoalcohol to the mixed solution. The molar ratio of the mercapto-tertiary amine compound to bromoalcohol is 1:1.5 - 2. Place it at room temperature and react for 12 - 36 hours. Remove the solvent by rotary evaporation. Then add water and dichloromethane for extraction. The organic phase is dried with anhydrous magnesium sulfate. Finally, obtain the tertiary amine-alcohol intermediate through filtration and rotary evaporation;
[0010] S2:
[0011]
[0012] Mix the tertiary amine-alcohol intermediate with thionyl chloride in a molar ratio of 1:1 - 5. Place it at 40 - 60 °C and react for 4 - 8 hours. Remove thionyl chloride by rotary evaporation to obtain tertiary amine-chloroalkane hydrochloride;
[0013] Prepare an aqueous solution of the tertiary amine-chloroalkane hydrochloride with a concentration of 0.1 - 0.5 g / ml. Mix the solution with sodium azide and place it at 80 °C and react for 18 - 48 hours to obtain the monomer compound. The molar ratio of the tertiary amine-chloroalkane hydrochloride to sodium azide is 1:2 - 6;
[0014] S3: Prepare a solution of the tertiary amine compound with a concentration of 10 - 50 g / l. Mix the solution with propargyl bromide and place it at 40 - 60 °C and react for 4 - 12 hours. Then obtain the sequence polymer G0.5 through post-treatment. The molar ratio of the tertiary amine compound to propargyl bromide is 1:1.2 - 2;
[0015] Subsequently, prepare a solution of the sequence polymer G0.5 with a concentration of 10 - 50 g / l. Mix it with the monomer compound obtained in step S2. Add a catalyst under the protection of an inert gas. Place it at 40 - 60 °C and react for 4 - 12 hours. Then obtain the sequence polymer G1 through post-treatment. The molar ratio of the sequence polymer G0.5 to the catalyst is 10 - 100:1. The molar ratio of the sequence polymer G0.5 to the monomer compound is 1:1.2 - 2;
[0016] S4: Prepare a solution of the sequence polymer G1 with a concentration of 10 - 50 g / L. Mix the solution with propargyl bromide and react at 40 - 60 °C for 4 - 12 hours. Then, obtain the sequence polymer G1.5 through post-treatment. The molar ratio of the tertiary amine compound to propargyl bromide is 1:1.2 - 2. Subsequently, prepare a solution of the sequence polymer G1.5 with a concentration of 10 - 50 g / l, mix it with the monomer compound obtained in step S2, add a catalyst under the protection of an inert gas, and react at 40 - 60 °C for 4 - 12 hours. Then, obtain the sequence polymer G2 through post-treatment. The molar ratio of the sequence polymer G1.5 to the catalyst is 10 - 100:1, and the molar ratio of the sequence polymer G1.5 to the monomer compound is 1:1.2 - 2;
[0017] S5: Repeat step S4 to obtain a sequence polymer.
[0018] Preferably, the mercapto-tertiary amine compound is one or more of 2-dimethylaminoethanethiol, 3-dimethylaminopropanethiol, and 2-diethylaminoethanethiol.
[0019] Preferably, the bromoalcohol compound is one of 2-bromoethanol, 3-bromopropanol, 4-bromobutanol, 5-bromopentanol, 6-bromohexanol, 7-bromoheptanol, 8-bromooctanol, 9-bromononanol, or 10-bromodecanol.
[0020] Preferably, the sodium hydroxide solution is one or more of an aqueous solution, a methanol solution, and an ethanol solution.
[0021] Preferably, the tertiary amine compound is dimethylpropylamine, dimethylbutylamine, dimethylethanolamine, or triethylamine.
[0022] Preferably, for the solution of the tertiary amine compound and the solution of the sequence polymer G1, the solvent is one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.
[0023] Preferably, the catalyst is one or more of cuprous chloride, cuprous bromide, or elemental copper.
[0024] Preferably, the post-treatment method is the precipitation method, and the precipitant is one or more of ether, ethyl acetate, acetone, or tetrahydrofuran.
[0025] Preferably, prepare a polymer solution with a concentration of 5 - 10 g / L from the sequence polymer G5 obtained in step S4. Mix the polymer solution with propargyl bromide and repeat the operations in step S4 1 - 8 times to obtain a sequence polymer.
[0026] The beneficial effects of the present invention are as follows:
[0027] (1) The present invention alternately performs copper-catalyzed azide-alkyne click reaction and quaternization reaction, and successfully prepares sequence-monodisperse polyionic liquids by the stepwise growth method. The sequence-monodisperse polyionic liquids have a single molecular weight distribution, clear and encodable structures, no by-products are generated during the reaction, the reaction conditions and purification methods are simple and easy to implement, and the yield is large.
[0028] (2) The sequence-monodisperse polymers prepared by the present invention have both cationicity and monodispersity, enabling them to have two advantages simultaneously, and having good application prospects in the fields of biomedicine, antistatic, electrode materials, etc.
[0029] (3) For the sequence-monodisperse polymers prepared by the present invention, the decoding of the polymer structure can be achieved through mass spectrometry detection to obtain the complete polymer structure. Through monomer design and selection, at least ten different data storages can be realized to achieve decimal encoding, which makes it have good application prospects in the field of molecular-level information transmission. Description of the Drawings
[0030] Figure 1 1H NMR spectrum of the monomer compound in Example 1, and each peak is clearly assigned;
[0031] Figure 2 13C NMR spectrum of the monomer compound in Example 1, and each peak is clearly assigned;
[0032] Figure 3 Aqueous gel permeation chromatography spectrum of polymer G7 in Example 1, and its molecular weight polydispersity is less than 1.05. Detailed Embodiments
[0033] The following are only the preferred embodiments of the present invention, and the protection scope is not limited to this embodiment. All technical solutions falling within the idea of the present invention shall belong to the protection scope of the present invention.
[0034] Example 1
[0035] This example provides a synthesis method of a sequence-encodable polymer, including the following steps:
[0036] Prepare a tertiary amine-alcohol type intermediate, and the synthesis route is as follows:
[0037]
[0038] The specific experimental steps are as follows: In a 250 - milliliter flask, add 40 milliliters of methanol, 40 milliliters of deionized water, 0.04 mole of N,N - dimethylethylthiolamine, 0.65 mole of 2 - bromoethanol, and 0.8 mole of sodium hydroxide in sequence. Stir the reaction at room temperature for 24 hours. The product is rotary - evaporated to remove the solvent at 60 °C, add 50 milliliters of water, extract with dichloromethane (50 milliliters * 3), collect the organic phase, dry it with anhydrous magnesium sulfate, and rotary - evaporate to remove the solvent to obtain the intermediate. The yield is 72%.
[0039] Prepare the monomer compound for synthesizing the sequence - coded polymer. The synthetic route is as follows:
[0040]
[0041] The specific experimental steps are as follows:
[0042] (1) Dissolve the intermediate obtained above in 40 milliliters of dichloromethane, slowly drop 0.08 milliliters of thionyl chloride under an ice - water bath condition, heat up to 40 °C, and reflux for 6 hours. Rotary - evaporate the product to remove the solvent and excess thionyl chloride, and wash the residual precipitate with ether (50 milliliters * 3). The yield is 98%.
[0043] (2) Dissolve the precipitate obtained above in 100 milliliters of water, add 0.08 mole of sodium azide, heat up to 80 °C, and stir the reaction for 24 hours. After the reaction is completed, add sodium hydroxide solution until the pH value reaches 11, extract with ether (100 milliliters * 3), collect the organic phase, dry it with anhydrous magnesium sulfate, and rotary - evaporate to remove the solvent to obtain the monomer compound required for synthesizing the sequence - coded polymer, which is a colorless liquid. The yield is 85%.
[0044] (3) Prepare the first - generation sequence - coded polymer
[0045] Dissolve 0.5 grams of triethylamine in 5 milliliters of N,N - dimethylformamide, mix it with 1 gram of propargyl bromide, react at 40 °C for 4 hours. The product is precipitated in 50 milliliters of ether, and the precipitate is collected by centrifugation to obtain the sequence polymer G0.5. Subsequently, dissolve 0.5 grams of the sequence polymer G0.5 in 3 milliliters of N,N - dimethylformamide, mix it with the monomer compound obtained in step (2), add copper(I) bromide under inert gas protection, and react at 40 °C for 4 hours. The product is precipitated in 50 milliliters of ether, and the precipitate is collected by centrifugation to obtain the sequence polymer G1. The molar ratio of the sequence polymer G0.5 to copper(I) bromide is 20:1, and the molar ratio of the sequence polymer G0.5 to the monomer compound is 1:1.2.
[0046] (4) Prepare the second - generation sequence - coded polymer
[0047] Dissolve the above-mentioned polymer G1 in 3 mL of N,N-dimethylformamide, mix it with 1.5 g of propargyl bromide, and react at 40 °C for 4 hours. The product is precipitated in 50 mL of diethyl ether, and the precipitate is collected by centrifugation to obtain the sequential polymer G1.5. Subsequently, dissolve the sequential polymer G1.5 in 3 mL of N,N-dimethylformamide, mix it with the monomer compound obtained in step (2), add cuprous bromide under the protection of an inert gas, and react at 40 °C for 4 hours. The product is precipitated in 50 mL of diethyl ether, and the precipitate is collected by centrifugation to obtain the sequential polymer G2. The molar ratio of the sequential polymer G1.5 to cuprous bromide is 20:1, and the molar ratio of the sequential polymer G1.5 to the monomer compound is 1:1.2.
[0048] (5) Repeat the above steps 6 times to obtain the seventh-generation sequentially encodable polymer.
[0049] Example 2
[0050] This example provides a method for synthesizing a sequentially encodable polymer, which includes the following steps:
[0051] (1) Prepare a tertiary amine-alcohol intermediate. The specific experimental steps are as follows: In a 250 mL flask, sequentially add 40 mL of methanol, 40 mL of deionized water, 0.04 mol of N,N-diethylethylthiolamine, 0.65 mol of 3-bromopropanol, and 0.8 mol of sodium hydroxide, and stir and react at room temperature for 24 hours. The product is rotary-evaporated to remove the solvent at 60 °C, 50 mL of water is added, and it is extracted with dichloromethane (50 mL × 3). The organic phase is collected, dried with anhydrous magnesium sulfate, and the solvent is removed by rotary evaporation to obtain the intermediate. The yield is 72%.
[0052] (2) Prepare the monomer compound for synthesizing the sequential polymer. The specific experimental steps are as follows:
[0053] Dissolve the above-obtained intermediate in 40 mL of dichloromethane, slowly add 0.08 mol of thionyl chloride dropwise under an ice-water bath, raise the temperature to 40 °C, and reflux for 6 hours. The product is rotary-evaporated to remove the solvent and excess thionyl chloride, and the residual precipitate is washed with diethyl ether (50 mL × 3). The yield is 98%.
[0054] Dissolve the above-obtained precipitate in 100 mL of water, add 0.08 mol of sodium azide, raise the temperature to 80 °C, and stir and react for 24 hours. After the reaction is completed, add sodium hydroxide solution to pH = 11, and extract with diethyl ether (100 mL × 3). The organic phase is collected, dried with anhydrous magnesium sulfate, and the solvent is removed by rotary evaporation to obtain the monomer compound required for synthesizing the sequential polymer, which is a colorless liquid. The yield is 85%.
[0055] (3) Prepare the first-generation sequentially encodable polymer
[0056] Dissolve 0.5 g of triethylamine in 5 mL of N,N-dimethylformamide, mix it with 1 g of propargyl bromide, react at 40 °C for 4 hours, precipitate the product in 50 mL of diethyl ether, collect the precipitate by centrifugation to obtain the sequence polymer G0.5. Subsequently, dissolve 0.5 g of the sequence polymer G0.5 in 3 mL of N,N-dimethylformamide, mix it with the monomer compound obtained in step (2), add cuprous bromide under inert gas protection, and react at 40 °C for 4 hours. The product is precipitated in 50 mL of diethyl ether, and the precipitate is collected by centrifugation to obtain the sequence polymer G1. The molar ratio of the sequence polymer G0.5 to cuprous bromide is 20:1, and the molar ratio of the sequence polymer G0.5 to the monomer compound is 1:1.2.
[0057] (4) Preparation of the second-generation sequence-encodable polymer
[0058] Dissolve the above polymer G1 in 3 mL of N,N-dimethylformamide, mix it with 1.5 g of propargyl bromide, react at 40 °C for 4 hours, precipitate the product in 50 mL of diethyl ether, collect the precipitate by centrifugation to obtain the sequence polymer G1.5. Subsequently, dissolve the sequence polymer G1.5 in 3 mL of N,N-dimethylformamide, mix it with the monomer compound obtained in step (2), add cuprous bromide under inert gas protection, and react at 40 °C for 4 hours. The product is precipitated in 50 mL of diethyl ether, and the precipitate is collected by centrifugation to obtain the sequence polymer G2. The molar ratio of the sequence polymer G1.5 to cuprous bromide is 20:1, and the molar ratio of the sequence polymer G1.5 to the monomer compound is 1:1.2.
[0059] (5) Repeat the above steps 3 times to obtain the fifth-generation sequence-encodable polymer.
[0060] Example 3
[0061] This example provides a method for synthesizing a sequence-encodable polymer, which includes the following steps:
[0062] (1) Preparation of the first-generation sequence-encodable polymer
[0063] Dissolve 0.5 g of dimethylethanolamine in 5 mL of N,N-dimethylformamide, mix it with 1 g of propargyl bromide, react at 40 °C for 4 hours, precipitate the product in 50 mL of diethyl ether, collect the precipitate by centrifugation to obtain the sequence polymer G0.5. Subsequently, dissolve 0.5 g of the sequence polymer G0.5 in 3 mL of N,N-dimethylformamide, mix it with the monomer compound obtained in step (2), add cuprous bromide under inert gas protection, and react at 40 °C for 4 hours. The product is precipitated in 50 mL of diethyl ether, and the precipitate is collected by centrifugation to obtain the sequence polymer G1. The molar ratio of the sequence polymer G0.5 to cuprous bromide is 20:1, and the molar ratio of the sequence polymer G0.5 to the monomer compound is 1:1.2.
[0064] (2) Prepare the second-generation sequence-encodable polymer
[0065] Dissolve the above-mentioned polymer G1 in 3 mL of N,N-dimethylformamide, mix it with 1.5 g of propargyl bromide, react at 40 °C for 4 hours, precipitate the product in 50 mL of diethyl ether, collect the precipitate by centrifugation, and obtain the sequence polymer G1.5. Subsequently, dissolve the sequence polymer G1.5 in 3 mL of N,N-dimethylformamide, mix it with the monomer compound obtained in step (2) of Example 2, add cuprous bromide under the protection of an inert gas, react at 40 °C for 4 hours, precipitate the product in 50 mL of diethyl ether, collect the precipitate by centrifugation, and obtain the sequence polymer G2. The molar ratio of the sequence polymer G1.5 to cuprous bromide is 20:1, and the molar ratio of the sequence polymer G1.5 to the monomer compound is 1:1.2.
[0066] (3) Repeat the above steps 3 times, alternately using the monomer compound obtained in Example 1 and the monomer compound obtained in Example 2, to obtain the fifth-generation sequence-encodable polymer.
[0067] The specific embodiments described above further elaborate on the technical problems solved, technical solutions, and beneficial effects of the present invention. It should be understood that the above are only specific embodiments of the present invention and are not used to limit the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.
Claims
1. A synthesis method of a sequence-encodable polyionic liquid, characterized in that, It includes the following steps: S1: Mix the mercapto-tertiary amine compound with a sodium hydroxide solution having a concentration of 2 - 6 mol / L. The molar ratio of the mercapto-tertiary amine compound to sodium hydroxide is 1:2 - 3. Add bromohydrin to the mixed solution. The molar ratio of the mercapto-tertiary amine compound to bromohydrin is 1:1.5 - 2. Place it at room temperature for reaction for 12 - 36 hours. Remove the solvent by rotary evaporation. Then add water and dichloromethane for extraction. The organic phase is dried with anhydrous magnesium sulfate. Finally, obtain the tertiary amine-alcohol intermediate through filtration and rotary evaporation; S2: Mix the tertiary amine-alcohol intermediate with thionyl chloride in a molar ratio of 1:1 - 5. Place it at 40 - 60 °C for reaction for 4 - 8 hours. Remove thionyl chloride by rotary evaporation to obtain tertiary amine-chloroalkane hydrochloride; Prepare an aqueous solution of the tertiary amine-chloroalkane hydrochloride with a concentration of 0.1 - 0.5 g / ml. Mix the solution with sodium azide and place it at 80 °C for reaction for 18 - 48 hours to obtain a monomer compound. The molar ratio of the tertiary amine-chloroalkane hydrochloride to sodium azide is 1:2 - 6; S3: Prepare a solution of the tertiary amine compound with a concentration of 10 - 50 g / l. Mix the solution with propargyl bromide and place it at 40 - 60 °C for reaction for 4 - 12 hours. Then obtain the sequence polymer G0.5 through post-treatment. The molar ratio of the tertiary amine compound to propargyl bromide is 1:1.2 - 2; Subsequently, prepare a solution of the sequence polymer G0.5 with a concentration of 10 - 50 g / l. Mix it with the monomer compound obtained in step S2. Add a catalyst under the protection of an inert gas. Place it at 40 - 60 °C for reaction for 4 - 12 hours. Then obtain the sequence polymer G1 through post-treatment. The molar ratio of the sequence polymer G0.5 to the catalyst is 10 - 100:
1. The molar ratio of the sequence polymer G0.5 to the monomer compound is 1:1.2 - 2; S4: Prepare a solution of the sequence polymer G1 with a concentration of 10 - 50 g / L. Mix the solution with propargyl bromide and place it at 40 - 60 °C for reaction for 4 - 12 hours. Then obtain the sequence polymer G1.5 through post-treatment. The molar ratio of the tertiary amine compound to propargyl bromide is 1:1.2 - 2; Subsequently, prepare a solution of the sequence polymer G1.5 with a concentration of 10 - 50 g / l. Mix it with the monomer compound obtained in step S2. Add a catalyst under the protection of an inert gas. Place it at 40 - 60 °C for reaction for 4 - 12 hours. Then obtain the sequence polymer G2 through post-treatment. The molar ratio of the sequence polymer G1.5 to the catalyst is 10 - 100:
1. The molar ratio of the sequence polymer G1.5 to the monomer compound is 1:1.2 - 2; S5: Repeat step S4 to obtain a sequence polymer; The mercapto-tertiary amine compound is one or more of 2-dimethylaminoethanethiol, 3-dimethylaminopropanethiol, 2-diethylaminoethanethiol; The bromoalcohol compound is 2-bromoethanol, 3-bromopropanol, 4-bromobutanol, 5-bromopentanol, 6-bromohexanol, 7-bromoheptanol, 8-bromooctanol, 9-bromononanol or 10-bromodecanol; The polydispersity of the obtained polyionic liquid is less than 1.
05.
2. The synthesis method of a sequence-encodable polyionic liquid according to claim 1, characterized in that, The sodium hydroxide solution is one or more of an aqueous solution, a methanol solution, and an ethanol solution.
3. A method for synthesizing a sequence-encodable polyionic liquid according to claim 1, characterized in that The tertiary amine compound is dimethylpropylamine, dimethylbutylamine, dimethylethanolamine, or triethylamine.
4. The synthesis method of a sequence-encodable polyionic liquid according to claim 1, characterized in that, The solutions of the tertiary amine compound and the sequence polymer G1 are both solvents of one or more of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.
5. A method for synthesizing a sequence-encodable polyionic liquid according to claim 1, characterized in that, The catalyst is one or more of cuprous chloride, cuprous bromide, or elemental copper.
6. A method for synthesizing a sequence-encodable polyionic liquid according to claim 1, characterized in that, The post-treatment method is a precipitation method, and the precipitant is one or more of diethyl ether, ethyl acetate, acetone, or tetrahydrofuran.
7. A method for synthesizing a sequence-encodable polyionic liquid according to claim 1, characterized in that, The sequence polymer G5 obtained in step S4 is formulated into a polymer solution with a concentration of 5-10 g / L, and the polymer solution is mixed with propargyl bromide, and the operation of step S4 is repeated 1-8 times to obtain a sequence polymer.