Preparation method of chiral polymer regulated by copolymerization of achiral monomer
Chiral polymers with achiral monomer copolymerization control can be prepared by using supramolecular template method to copolymerize with achiral monomers. This solves the problems of cumbersome process and high cost in the preparation of chiral polymers in the existing technology, and realizes flexible chiral control and efficient preparation of multifunctional polymers, which are applicable to fields such as circularly polarized luminescence and chiral recognition.
Patent Information
- Application Number
- CN202210405303.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-04-18
- Publication Date
- 2025-10-28
- Estimated Expiration
- 2042-04-18
AI Technical Summary
Existing technologies require the pre-synthesis of template molecules with different chiralities when preparing chiral polymers, which makes the synthesis process cumbersome and costly, and the control mode is inflexible, affecting the preparation efficiency of chiral products and their application range.
A supramolecular template method was adopted, using a single chiral amphiphilic small molecule as a template agent and phenylenediamine as the initial monomer. By introducing an achiral monomer to copolymerize with the initial monomer, and then performing extraction and vacuum drying, a chiral polymer with achiral monomer copolymerization control was prepared.
This invention enables the controllable preparation of left-handed, right-handed, or non-helical multifunctional polymers in enantiomeric pure template systems, simplifying the preparation process, reducing costs, and improving preparation efficiency. It has excellent application prospects in the fields of circularly polarized luminescence, enantiomeric separation, and chiral recognition.
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Figure CN116948170B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of nanomaterial preparation technology, and in particular to a method for preparing chiral polymers controlled by copolymerization of non-chiral monomers. Background Technology
[0002] Chirality is a fundamental characteristic of nature, and its dynamic self-differentiation is widely present in organisms, such as L-amino acids and D-polysaccharides. In the past few decades, significant progress has been made in the field of supramolecular chirality regulation. Specifically, external stimuli, such as pH, temperature, light, solvents, and metal ions, can reconstruct various non-covalent interactions between stacking units, thereby amplifying or even reversing supramolecular chirality. To date, this regulation has primarily focused on supramolecular soft gels. For some harsh application environments, chiral covalent polymers may be more suitable due to their better environmental tolerance.
[0003] Chiral polymers can be classified into two categories based on whether their active monomers contain chiral centers: one category contains chiral centers, whose monomer chirality can be directly derived into the entire polymer framework; the other category does not contain chiral centers, but whose monomers can be generated into macroscopic helical structures under the constraint of an external chiral template. In function-oriented applications, achiral monomers have greater potential due to their richer diversity.
[0004] In the prior art, monochiral polymer nanomaterials have been successfully prepared using the traditional supramolecular template method. Chinese Patent Application No. 201410278615.0, published on March 2, 2016, entitled "A Method for Preparing Monochiral Helical Carbon Nanotubes," uses a supramolecular assembly of long-chain acylated amino acids as a template. Monochiral phenolic resin nanotubes are obtained by polymerizing the precursor 3-aminophenol and formaldehyde on the template surface, and finally, monochiral carbon materials are obtained through high-temperature carbonization. Chinese Patent Application No. 201210001654.7, published on July 4, 2012, entitled "A Method for Preparing Helical Bipyridyl Bridged Polysilsesquioxane Nanomaterials," discloses the successful preparation of monochiral helical polysilsesquioxanes with high elasticity and heat resistance under acidic conditions using a cationic chiral surfactant as a template agent and a bipyridyl bridged polysilsesquioxane as a silicon source. In the above preparation method, the chirality of the final product is determined by the chirality of the template molecule, and only a product with a single chirality can be obtained. However, in practical applications, it is usually necessary to obtain polymers with different chirities. In this case, when using the above method to prepare products with different chirities, it is necessary to synthesize template molecules with different chirities in advance. This synthesis process is cumbersome and increases the cost of preparing chiral polymers.
[0005] In the prior art, Chinese patent application No. 202011251406.9, published on March 1, 2022, entitled "Metal Ion-Regulated Chiral Materials and Their Preparation Methods," employs a supramolecular template method. It uses chiral small molecule self-assemblies as template agents and monomers and aldehydes as precursors, conducting a co-assembly reaction mediated by metal ions to ultimately obtain metal ion-mediated nanomaterials with microscopic helical structures and optical activity. In this technical solution, metal ions disrupt the hydrogen bond network of the chiral template, re-forming a chiral assembly matching the metal ions. The monomer then reacts with the chiral assembly to obtain nanomaterials with the desired chirality. However, the essence of this solution lies in using metal ions to pre-prepare an intermediate chiral template with chirality consistent with the final product, and then further obtaining the pre-prepared product. While this preparation method can regulate the chirality of the final product, the regulation mode is inflexible and the composition of the obtained product is relatively simple, affecting the preparation efficiency and application range of the chiral product.
[0006] In view of this, it is necessary to design an improved method for preparing chiral polymers controlled by non-chiral monomer copolymerization in order to solve the above problems. Summary of the Invention
[0007] The purpose of this invention is to provide a method for preparing chiral polymers controlled by non-chiral monomer copolymerization.
[0008] To achieve the above-mentioned objectives, this invention provides a method for preparing a chiral polymer controlled by copolymerization of achiral monomers. The chiral polymer is prepared using a supramolecular template method, employing a single-chiral amphiphilic small molecule as a template agent and phenylenediamine as the initial monomer. The method involves introducing an achiral monomer to copolymerize with the initial monomer, followed by extraction and vacuum drying. The method includes the following steps:
[0009] S1. Dissolve the single-chiral amphiphilic small molecule, the initial monomer, and the non-chiral comonomer in an organic solvent according to a predetermined ratio to obtain a mixed solution; then, add a predetermined amount of deionized water to the mixed solution at a predetermined temperature, stir at a constant temperature for a certain time, and then add a predetermined amount of oxidant to induce a copolymerization reaction.
[0010] S2. After the copolymerization reaction in step S2 is completed, the product of the copolymerization reaction is subjected to vacuum filtration and extraction, and then vacuum drying to obtain the chiral polymer controlled by the non-chiral monomer copolymerization.
[0011] Preferably, in step S1, the non-chiral comonomer comprises, but is not limited to, one or more of 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyridine, 2,3-diaminopyridine, 3,4-diaminopyridine, 3,5-diaminopyridine, o-aminopyridine, m-aminopyridine, p-aminopyridine, and 2-amino-6-methylpyridine.
[0012] Preferably, in step S1, the phenylenediamine is one of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine, and the single-chiral amphiphilic small molecule is one of enantiomeric pure L-type template molecule and D-type template molecule.
[0013] Preferably, in step S1, the oxidant is ammonium persulfate, and the molar ratio of the single-chiral amphiphilic small molecule, the phenylenediamine, the non-chiral comonomer, the organic solvent, the deionized water, and the persulfate is 1:(5-40):(0.1-5):(1000-8000):(3000-60000):(5-160).
[0014] Preferably, the organic solvent is one or more selected from ethanol, methanol, acetonitrile, dimethyl sulfoxide, 1,4-dioxane, and tetrahydrofuran.
[0015] Preferably, the persulfide is one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.
[0016] Preferably, in step S1, the predetermined temperature is 15–60°C, and the stirring time is 10–40 min.
[0017] Preferably, in step S1, the reaction time of the copolymerization reaction is 30 to 120 minutes.
[0018] Preferably, in step S2, the extraction process uses ethanol as the extractant, the extraction time is 24-48 hours, and the vacuum drying temperature is 30-50°C.
[0019] Preferably, the chirality of the chiral polymer regulated by the copolymerization of the achiral monomer is one of a left-handed helical structure, a right-handed helical structure, and an achiral helical structure.
[0020] The beneficial effects of this invention are:
[0021] 1. The present invention provides a method for preparing chiral polymers with achiral monomer copolymerization control. Using a single-chiral amphiphilic small molecule as a template agent, phenylenediamine as the initial monomer, aminopyridine and its derivatives as achiral monomers, and persulfide as an oxidant to initiate the polymerization of the initial monomer and the achiral comonomer on a chiral template surface, the method then proceeds with extraction and vacuum drying to obtain the chiral polymer with achiral monomer copolymerization control. Simultaneously, by using different types of achiral monomers to control the chiral structure of the obtained polymer, left-handed helical, right-handed helical, or non-helical achiral monomer copolymerization micro-controllable chiral polymers can be controllably prepared. The chiral polymers with achiral monomer copolymerization control prepared using the method provided by the present invention have excellent application prospects in fields such as circularly polarized luminescence, enantiomeric separation, and chiral recognition.
[0022] 2. The method for preparing chiral polymers regulated by achiral monomer copolymerization provided by this invention utilizes hydrogen bonds between achiral monomers and template molecules to regulate the chiral microstructure of the supramolecular template, thereby regulating the chiral structure of the final chiral polymer. Before the addition of the oxidizing agent persulfide, the microstructure within the supramolecular transcription system is dynamically controllable, and can be a left-handed, right-handed, or achiral structure. Through the above method, multifunctional polymers with left-handed helices, right-handed helices, or non-helices can be controllably prepared using a single chiral template molecule. The mechanism of using achiral monomers to regulate the chiral structure of the obtained polymer is as follows: the inherent hydrogen bonds between the achiral monomer and the template molecule overcome the electrostatic interaction between the template molecule and the phenylenediamine molecule and the inherent chirality of the template molecule itself, thereby changing the supramolecular stacking mode of the entire system and generating chirality independent of the template molecule, thus regulating the chirality of the polymer.
[0023] 3. The method for preparing chiral polymers with achiral monomer copolymerization control provided by the present invention can controllably prepare achiral polymers with achiral monomer copolymerization microcontrollers in an enantiomeric pure template system. This method has the advantages of simple preparation process, low cost and high preparation efficiency, and is expected to have good application performance in the fields of enantiomeric separation, chiral sensing and circularly polarized luminescence. Attached Figure Description
[0024] Figure 1 The image shows a SEM image of the 2,6-diaminopyridine-regulated left-handed helical polymer provided in Example 1 of this invention, with a scale bar of 100 nm.
[0025] Figure 2 The image shows a SEM image of the right-handed helical polymer provided in Comparative Example 1 of this invention, with a scale bar of 100 nm.
[0026] Figure 3SEM image of the 2,6-diaminopyridine-regulated right-handed helical polymer provided in Example 2 of the present invention, with a scale bar of 100 nm;
[0027] Figure 4 The image shows a SEM image of the left-handed helical polymer provided in Comparative Example 2 of this invention, with a scale bar of 100 nm.
[0028] Figure 5 SEM image of the 2,4-diaminopyridine-regulated left-handed helical polymer provided in Example 3 of the present invention, with a scale bar of 200 nm;
[0029] Figure 6 The image shows a SEM image of the 2,3-diaminopyridine-regulated right-handed helical polymer provided in Example 4 of this invention, with a scale bar of 100 nm.
[0030] Figure 7 The image shows a SEM image of the 2,5-diaminopyridine-regulated nanorod polymer provided in Example 5 of this invention, with a scale bar of 100 nm.
[0031] Figure 8 SEM image of the 3,4-diaminopyridine-regulated flat nanoribbon polymer provided in Example 6 of this invention, with a scale bar of 500 nm;
[0032] Figure 9 SEM image of the o-aminopyridine-regulated left-handed helical polymer provided in Example 7 of the present invention, with a scale bar of 1 μm;
[0033] Figure 10 The image shows a SEM image of the straight tubular polymer regulated by 2-amino-6-methylpyridine provided in Example 8 of this invention. The scale bar is 2 μm. Detailed Implementation
[0034] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
[0035] It should also be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and / or processing steps closely related to the present invention are shown in the accompanying drawings, while other details that are not closely related to the present invention are omitted.
[0036] Additionally, it should be noted that the terms “comprising,” “including,” or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0037] Please see Figure 1As shown, this invention provides a method for preparing chiral polymers regulated by achiral monomer copolymerization. The achiral monomer copolymerization-regulated chiral polymers are prepared using a supramolecular template method, with a single-chiral amphiphilic small molecule as the template agent and phenylenediamine as the initial monomer. The method involves introducing an achiral monomer to copolymerize with the initial monomer, followed by extraction and vacuum drying. The method includes the following steps:
[0038] S1. Dissolve the single-chiral amphiphilic small molecule, the initial monomer, and the non-chiral comonomer in an organic solvent according to a predetermined ratio to obtain a mixed solution; then, add a predetermined amount of deionized water to the above mixed solution at a predetermined temperature, stir at a constant temperature for a certain time, and then add a predetermined amount of ammonium persulfate to carry out a copolymerization reaction.
[0039] S2. After the copolymerization reaction in step S2 is completed, the product of the copolymerization reaction is subjected to vacuum filtration and extraction, and then vacuum drying to obtain the chiral polymer controlled by the copolymerization of non-chiral monomers.
[0040] Preferably, in step S1, the monochiral amphiphilic small molecule is one of an enantiomeric pure L-type (left-handed) template molecule or a D-type (right-handed) template molecule;
[0041] Preferably, in step S1, the phenylenediamine is one of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine;
[0042] Preferably, in step S1, the structural formula of the monochiral amphiphilic small molecule is as follows:
[0043]
[0044] Where R1 is C n H 2n+1 , n=12~18; R2 includes but is not limited to CH3, C6H5, CH2C6H5, C8NH6(CH2)2COOH, CH2COOH, (CH2)4NH2, CH(CH3)CH2CH3, CH(CH3)2C3H6, (CH2)3NHC(NH)NH2.
[0045] Preferably, in step S1, the organic solvent is one or more of ethanol, methanol, acetonitrile, dimethyl sulfoxide, 1,4-dioxane, and tetrahydrofuran.
[0046] Preferably, in step S1, the molar ratio of the monochiral amphiphilic small molecule: phenylenediamine: non-chiral comonomer: organic solvent: deionized water: persulfide is 1:(5-40):(0.1-5):(1000-8000):(3000-60000):(5-160).
[0047] Preferably, in step S1, the non-chiral comonomer includes, but is not limited to, one or more of 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyridine, 2,3-diaminopyridine, 3,4-diaminopyridine, 3,5-diaminopyridine, o-aminopyridine, m-aminopyridine, p-aminopyridine, and 2-amino-6-methylpyridine.
[0048] Preferably, in step S1, the persulfide is one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.
[0049] Preferably, in step S1, the predetermined temperature is 15–60°C; and the stirring time is 10–40 min.
[0050] Preferably, in step S1, the reaction time of the copolymerization reaction is 30 to 120 minutes.
[0051] Preferably, in step S2, ethanol is used as the extraction solvent, the extraction time is 24-48 hours, and the vacuum drying temperature is 30-50°C.
[0052] The preparation method of the chiral polymer regulated by non-chiral monomer copolymerization according to the present invention will be described below with reference to specific embodiments:
[0053] Example 1
[0054] S1, 0.050 mmol of a single-chiral amphiphilic small molecule D-PhgC 16 (R1=16, R2=C6H5), 0.66 mmol m-phenylenediamine and 0.075 mmol 2,6-diaminopyridine were dissolved in a mixed solution of 2 ml dimethyl sulfoxide and 4 ml acetonitrile; then, 30 ml deionized water was added at room temperature, and after stirring for 15 min, 0.148 mol / L ammonium persulfate aqueous solution was added to the entire reaction system, and the reaction was allowed to proceed for 120 min;
[0055] S2. After the reaction in step S1 is complete, filter the reaction product to obtain a solid product, and then remove the monochiral amphiphilic small molecule D-PhgC by Soxhlet extraction with ethanol solution for 24 hours. 16 Finally, the 2,6-diaminopyridine-regulated left-handed helical polymer was obtained by vacuum drying at 30°C. The SEM image of the polymer is shown below. Figure 1 As shown in the figure, the polymer has a left-handed helical structure with a diameter of 90–130 nm and a pitch of 100–200 nm. The results indicate that a left-handed helical polymer was successfully prepared using a D-type template molecule under the control of 2,6-diaminopyridine.
[0056] Comparative Example 1
[0057] The only difference between Comparative Example 1 and Example 1 is that the non-chiral monomer 2,6-diaminopyridine is not added. The other steps are basically the same as in Example 1 and will not be repeated here. The SEM image of the right-handed helical polymer obtained in Comparative Example 1 is shown below. Figure 2 As shown in the figure, the polymer has a right-handed helical structure with a diameter of 70-90 nm and a pitch of 200-300 nm. The results indicate that, without the regulation of 2,6-diaminopyridine, the helicity of the polymer follows the chirality of the D-type template molecule.
[0058] Example 2
[0059] The only difference between Example 2 and Example 1 is that Example 2 uses the single-chiral amphiphilic small molecule L-PhgC. 16 Using (R1 = 16, R2 = C6H5) as the template molecule, the other steps are basically the same as in Example 1, and will not be repeated here. The SEM image of the 2,6-diaminopyridine-regulated right-handed helical polymer obtained in Example 2 is shown below. Figure 3 As shown in the figure, the polymer has a right-handed helical structure with a diameter of 90–130 nm and a pitch of 100–200 nm. The results indicate that a right-handed helical polymer was successfully prepared using an L-type template molecule under the control of 2,6-diaminopyridine.
[0060] Comparative Example 2
[0061] The only difference between Comparative Example 2 and Example 2 is that the non-chiral monomer 2,6-diaminopyridine is not added; the other steps are basically the same as in Example 1 and will not be repeated here. The SEM image of the right-handed helical polymer obtained in Comparative Example 2 is shown below. Figure 4 As shown in the figure, the polymer has a left-handed helical structure with a diameter of 70–90 nm and a pitch of 200–300 nm. The results indicate that, without the regulation of 2,6-diaminopyridine, the helicity of the obtained polymer follows the chirality of the L-type template molecule.
[0062] Please see Figures 1 to 4 As shown, the experimental results of Comparative Examples 1, 2, 1, and 2 are compared. The results show that in the traditional supramolecular template method, the chirality of the obtained product corresponds one-to-one with the chirality of the template molecule. However, by introducing a non-chiral monomer to undergo a copolymerization reaction with m-phenylenediamine, this invention can selectively obtain polymers whose chirality is reversed compared to that of the template molecule. In this preparation process, no additional chirality modifier is needed, and left-handed and right-handed helical polymers can be prepared in an enantiomeric pure template system.
[0063] Example 3
[0064] The only difference between Example 3 and Example 1 is that 2,4-diaminopyridine is used as the achiral monomer. The other steps are basically the same as in Example 1 and will not be repeated here. The SEM image of the left-handed helical polymer obtained in Example 3 is shown below. Figure 5 As shown in the figure, the polymer has a left-handed helical structure with a diameter of 90–130 nm and a pitch of 100–200 nm. The results indicate that a left-handed helical polymer was successfully prepared using a D-type template molecule under the control of 2,4-diaminopyridine.
[0065] Example 4
[0066] The only difference between Example 4 and Example 1 is that 2,3-diaminopyridine is used as the achiral monomer. The other steps are basically the same as in Example 1 and will not be repeated here. The SEM image of the left-handed helical polymer obtained in Example 4 is shown below. Figure 6 As shown in the figure, the polymer has a left-handed helical structure with a diameter of 90-130 nm and a pitch of 100-200 nm. The results indicate that, under the control of 2,3-diaminopyridine, this embodiment successfully prepared a left-handed helical polymer using a D-type template molecule.
[0067] Example 5
[0068] The only difference between Example 5 and Example 1 is that 2,5-diaminopyridine is used as the achiral monomer. The other steps are basically the same as in Example 1 and will not be repeated here. The SEM image of the polymer obtained in Example 5 is shown below. Figure 7 As shown in the figure, the polymer does not exhibit a clear chiral configuration; it has a nanorod-like structure with a diameter of 30–50 nm. Please refer to [link / reference]. Figure 7 and combined Figure 1 , Figure 3 , Figure 5 and Figure 6 Compared with Examples 1 to 5, only the polymer obtained in Example 5 did not have a clear chiral configuration. This is mainly because, compared with 2,3 / 2,4 / 2,6-diaminopyridine, the relative positions between the two amino groups of 2,5-diaminopyridine are far apart, which may cause the interaction between the template molecule, m-phenylenediamine and diaminopyridine to not match the space required to form a helical structure. Therefore, the corresponding helical polymer could not be obtained. The above results show that the relative positions of the two amino groups in the introduced diaminopyridine are closely related to the morphology of the obtained polymer.
[0069] Example 6
[0070] The only difference between Example 6 and Example 1 is that 3,4-diaminopyridine is used as the achiral monomer. The other steps are basically the same as in Example 1 and will not be repeated here. The SEM image of the polymer obtained in Example 6 is shown below. Figure 8As shown in the figure, the polymer exhibits no obvious chiral configuration and instead presents a flat, nanoribbon-like structure. (Please refer to...) Figure 8 and combined Figure 1 , Figure 3 , Figure 5 and Figure 6 Compared with Examples 1 to 5, only the polymer obtained in Example 6 did not have a clear chiral configuration. This is mainly because, compared with 2,3 / 2,4 / 2,6-diaminopyridine, neither of the two amino groups of 3,4-diaminopyridine is in the ortho position of pyridine N. The above results indicate to some extent that the ortho amino group plays an important role in forming a product with a helical structure.
[0071] Example 7
[0072] The only difference between Example 7 and Example 1 is that o-aminopyridine is used as the achiral monomer; the other steps are basically the same as in Example 1 and will not be repeated here. The SEM image of the polymer obtained in Example 7 is shown below. Figure 9 As shown in the figure, the polymer exhibits a left-handed helical structure overall, but it is not uniform, with a diameter ranging from 100 to 900 nm and a pitch ranging from 150 to 100 nm. Please refer to [link / reference]. Figure 9 and Figure 8 Comparing the results of Example 7 and Example 6, the results show that a product with a helical structure was successfully prepared under the control of ortho-aminopyridine in this example. The above results indicate that the ortho-amino group of pyridine N plays an important role in the formation of a product with a helical structure.
[0073] Example 8
[0074] The only difference between Example 8 and Example 1 is that 2-amino-6-methylpyridine is used as the achiral monomer. The other steps are basically the same as in Example 1 and will not be repeated here. The SEM image of the polymer obtained in Example 8 is shown below. Figure 10 As shown in the figure, the polymer has a rectangular tubular structure with a diameter of 500–2000 nm. The inability to obtain a chiral polymer in this embodiment using 2-amino-6-methylpyridine is mainly due to the presence of an ortho-methyl group (relative to pyridine N) in the molecular structure of 2-amino-6-methylpyridine. The high steric hindrance of the methyl group may affect the interaction between the template, m-phenylenediamine, and 2-amino-6-methylpyridine, thus preventing the assembly of a long and ordered helical structure. Consequently, only a straight tubular polymer can be prepared.
[0075] In summary, this invention provides a method for preparing chiral polymers with achiral monomer copolymerization control. This invention employs a supramolecular template method, using enantiomeric pure, single-chiral amphiphilic small molecules as template agents, phenylenediamine as the initial monomer, and persulfides as oxidants. By introducing a series of achiral monomers of aminopyridine and its derivatives into the above reaction system and copolymerizing them with phenylenediamine, the microscopic chiral structure of the resulting polymer can be controlled. The chiral control process of the polymer mainly proceeds according to the following mechanism: the strong hydrogen bonds between the achiral monomer and the template molecule can overcome the electrostatic interaction between the template molecule and the phenylenediamine molecule and the inherent chirality of the template molecule itself, thereby determining the supramolecular stacking mode of the entire system, i.e., achieving supramolecular chirality independent of the template molecule's chirality. This allows for the controlled preparation of left-handed helical, right-handed helical, and non-helical polymers within a single-chiral template system. The chiral polymers prepared by the method provided in this invention, which are achiral monomer copolymers, have excellent applications in fields such as circularly polarized luminescence, enantiomeric separation, and chiral recognition due to their chiral configurations that can be regulated by achiral monomer copolymerization.
[0076] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims
1. A method for preparing a chiral polymer regulated by non-chiral monomer copolymerization, characterized in that, The chiral polymer regulated by the copolymerization of the achiral monomer is prepared by a supramolecular template method, using a single chiral amphiphilic small molecule as a template agent and phenylenediamine as the initial monomer. The copolymerization reaction is carried out by introducing a achiral monomer and the initial monomer, followed by extraction and vacuum drying. The preparation includes the following steps: S1. Dissolve the single-chiral amphiphilic small molecule, the initial monomer, and the achiral monomer in an organic solvent according to a predetermined ratio to obtain a mixed solution; then, add a predetermined amount of deionized water to the mixed solution at a predetermined temperature, stir at a constant temperature for a certain time, and then add a predetermined amount of oxidant to induce a copolymerization reaction. The non-chiral monomer is one or more of 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminopyridine, 2,3-diaminopyridine, 3,4-diaminopyridine, 3,5-diaminopyridine, o-aminopyridine, m-aminopyridine, p-aminopyridine, and 2-amino-6-methylpyridine. The phenylenediamine is one of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine, and the monochiral amphiphilic small molecule is one of enantiomeric pure L-type template molecule and D-type template molecule; The oxidant is ammonium persulfate, and the molar ratio of the single-chiral amphiphilic small molecule, the phenylenediamine, the achiral monomer, the organic solvent, the deionized water, and the ammonium persulfate is 1:(5-40):(0.1-5):(1000-8000):(3000-60000):(5-160). S2. After the copolymerization reaction in step S2 is completed, the product of the copolymerization reaction is subjected to vacuum filtration and extraction, and then vacuum drying to obtain the chiral polymer controlled by the non-chiral monomer copolymerization.
2. The method for preparing a chiral polymer regulated by non-chiral monomer copolymerization according to claim 1, characterized in that, The organic solvent is one or more of ethanol, methanol, acetonitrile, dimethyl sulfoxide, 1,4-dioxane, and tetrahydrofuran.
3. The method for preparing a chiral polymer regulated by non-chiral monomer copolymerization according to claim 1, characterized in that, In step S1, the predetermined temperature is 15-60°C, and the stirring time is 10-40 min.
4. The method for preparing a chiral polymer controlled by non-chiral monomer copolymerization according to claim 1, characterized in that, In step S1, the reaction time of the copolymerization reaction is 30 to 120 minutes.
5. The method for preparing a chiral polymer controlled by non-chiral monomer copolymerization according to claim 1, characterized in that, In step S2, the extraction process uses ethanol as the extractant, the extraction time is 24-48 hours, and the vacuum drying temperature is 30-50°C.
6. The method for preparing a chiral polymer regulated by non-chiral monomer copolymerization according to claim 1, characterized in that, The chiral structure of the chiral polymer regulated by the copolymerization of the achiral monomer is one of the following: left-handed helical structure, right-handed helical structure, and achiral helical structure.
Citation Information
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