Polyrotaxane with controllable cyclodextrin coverage rate as well as preparation method and application of polyrotaxane

Abstract

The invention discloses polyrotaxane with controllable cyclodextrin coverage rate as well as a preparation method and application of the polyrotaxane, and belongs to the technical field of polyrotaxane materials. The preparation method comprises the following steps: dissolving alpha-cyclodextrin, 3-hydroxyadamantane-1-carboxylic acid and polyethylene glycol diamine in deionized water, refrigerating and assembling to form quasi-polyrotaxane, and blocking to obtain polyrotaxane; wherein the polyethylene glycol diamine is prepared from polyethylene glycol and N, N '-carbonyldiimidazole, and the cyclodextrin coverage rate of the polyrotaxane is directionally regulated and controlled by regulating and controlling the mass ratio of the alpha-cyclodextrin to the 3-hydroxyadamantane-1-carboxylic acid, the adding sequence of the 3-hydroxyadamantane-1-carboxylic acid and the refrigerating and assembling time. Based on the mechanism that 3-hydroxyadamantane-1-carboxylic acid and polyethylene glycol compete in a cyclodextrin cavity, polyrotaxane with a cyclodextrin coverage rate of 0.5-2.5% is synthesized, and a polymer based on the polyrotaxane has better ductility and mechanical properties.

Description

Technical Field

[0001] The present invention belongs to the technical field of polyrotaxane materials, and more specifically, relates to a polyrotaxane with controllable cyclodextrin coverage, a preparation method and an application thereof. Background Art

[0002] Polyrotaxane (PR) is a classic supramolecular compound with a mechanical interlocking structure. It has a dynamic topological structure and a stable polymer skeleton. It is widely used in gels, elastomers, battery adhesives, solid electrolytes, biomedicine and other fields. Cyclodextrin, as a macrocyclic molecule, is widely used in the synthesis of polyrotaxanes. In the selection of guest molecules, α-cyclodextrin and polyethylene glycol match in size, and polyrotaxanes based on these two host-guest molecules have been greatly developed and applied.

[0003] In order to define the number of α-cyclodextrins on the polyethylene glycol chain, Harada et al. proposed the concept of cyclodextrin coverage ratio (CD coverage ratio) (Harada A, Li J, Kamachi M. Preparation and properties of inclusion complexes of polyethylene glycol with alpha-cyclodextrin [J]. Macromolecules, 1993, 26 (21): 5698-5703). When the cyclodextrin coverage ratio is low, there is a longer sliding distance on the PEG chain, which can release more network stress and has lower hysteresis. When the cyclodextrin coverage ratio is low, the cross-linked polyrotaxane forms a molecular pulley structure, and the cyclodextrin has a longer sliding distance on the polyethylene glycol backbone, which can release more network stress, so that the prepared material has better ductility. When the coverage ratio of cyclodextrin is 2%, a large amount of PEG backbone is exposed, and strain-induced crystallization is generated during the stretching process, further enhancing the mechanical properties of the material.

[0004] However, the early methods of regulating the coverage of cyclodextrins were to control the temperature of the reaction process, use mixed solvents, etc. during the end-capping process, which was time-consuming or dangerous. Therefore, it is of great significance to develop a green, pollution-free, safe, fast, and controllable method for preparing low-coverage polyrotaxanes. Summary of the invention

[0005] In view of the above problems existing in the prior art, the technical problem to be solved by the present invention is to provide a method for preparing a polyrotaxane with controllable cyclodextrin coverage, based on the mechanism of competition between 3-hydroxyadamantane-1-carboxylic acid and polyethylene glycol in the cyclodextrin cavity, to synthesize a polyrotaxane with low CD coverage. Another technical problem to be solved by the present invention is to provide a polyrotaxane prepared by the above method, which has better mechanical properties. Another technical problem to be solved by the present invention is to provide the application of the above polyrotaxane in gel materials, elastomeric materials, battery adhesives, solid electrolytes, and biopharmaceutical materials.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is as follows:

[0007] A method for preparing a polyrotaxane with controllable cyclodextrin coverage, wherein α-cyclodextrin, 3-hydroxyadamantane-1-carboxylic acid and polyethylene glycol diamine are dissolved in deionized water and assembled in cold storage to form a pseudo-polyrotaxane, and the polyrotaxane is obtained by end-capping; wherein the polyethylene glycol diamine is prepared from polyethylene glycol and N,N'-carbonyldiimidazole, and the cyclodextrin coverage of the polyrotaxane is controlled by regulating the mass ratio of α-cyclodextrin and 3-hydroxyadamantane-1-carboxylic acid, the order of adding 3-hydroxyadamantane-1-carboxylic acid, and the cold storage assembly time. The cyclodextrin coverage of the obtained polyrotaxane is 0.5-2.5%.

[0008] Preferably, the preparation process of the polyethylene glycol diamine is as follows: under the protection of an inert gas, polyethylene glycol is dissolved in anhydrous tetrahydrofuran, N,N'-carbonyldiimidazole and ethylenediamine are added, and drying is performed after the reaction is completed to obtain polyethylene glycol diamine.

[0009] Preferably, the average molecular weight of the polyethylenediamine is 10,000.

[0010] Preferably, the g / g / mL ratio of polyethylenediamine, N,N'-carbonyldiimidazole and ethylenediamine is 10:0.85:1. The reaction temperature is 50°C.

[0011] Preferably, the mass ratio of the α-cyclodextrin, 3-hydroxyadamantane-1-carboxylic acid and polyethylene glycol diamine is 100:14.4 to 1:20.

[0012] Preferably, the temperature of the refrigerated assembly is 4°C, and the time of the refrigerated assembly is 24h or 48h.

[0013] Preferably, the order of adding the 3-hydroxyadamantane-1-carboxylic acid is as follows: first, 3-hydroxyadamantane-1-carboxylic acid and α-cyclodextrin are added for pre-assembly, then polyethylene glycol diamine is added for refrigerated assembly, and after the pseudopolyalkane is obtained, 3-hydroxyadamantane-1-carboxylic acid is added for end-capping reaction.

[0014] Preferably, the mass ratio of 3-hydroxyadamantane-1-carboxylic acid added in the pre-assembly to 3-hydroxyadamantane-1-carboxylic acid added in the end-capping reaction is 1 to 14.4:12.

[0015] The method for preparing the polyrotaxane with controllable cyclodextrin coverage specifically comprises the following steps:

[0016] 1) Under the protection of inert gas, polyethylene glycol is dissolved in anhydrous tetrahydrofuran, N,N'-carbonyldiimidazole is first added to react, and ethylenediamine is added dropwise to react after the reaction is completed to obtain a reaction liquid; the obtained reaction liquid is added dropwise to ether, filtered, and the precipitate is dissolved with dichloromethane, and then added dropwise to ether again, the precipitate is filtered, and dried to obtain polyethylene glycol diamine;

[0017] 2) dissolving α-cyclodextrin in deionized water, adding 3-hydroxyadamantane-1-carboxylic acid after it is completely dissolved, stirring until it is completely dissolved, adding the polyethylene glycol diamine prepared in step 1), stirring until the transparency of the system decreases, and refrigerating and assembling to prepare a pseudopolyrotaxane;

[0018] 3) dissolving 3-hydroxyadamantane-1-carboxylic acid and 4-(4,6-dimethoxytriazine-2-yl)-4-methylmorpholine hydrochloride in deionized water, adding the pseudopolyrotaxane obtained in step 2) above, mechanically stirring at room temperature for 24 hours, then adding 4-(4,6-dimethoxytriazine-2-yl)-4-methylmorpholine hydrochloride, continuing the reaction for 12 hours, removing water in the system by rotary evaporation, and adding dimethyl sulfoxide to obtain a transparent liquid;

[0019] 4) The transparent liquid obtained in step 3) is dialyzed in deionized water for two days using a dialysis bag, the water is changed 5-6 times, and freeze-dried to obtain a cyclodextrin-covered polyrotaxane.

[0020] Preferably, in step 3), the mass ratio of the 4-(4,6-dimethoxytriazine-2-yl)-4-methylmorpholine hydrochloride added for the first time to the 4-(4,6-dimethoxytriazine-2-yl)-4-methylmorpholine hydrochloride added for the second time is 2:1.

[0021] The method for preparing a polyrotaxane with controllable cyclodextrin coverage is used to prepare a polyrotaxane.

[0022] The polyrotaxane has the following structural formula:

[0023]

[0024] ; Wherein, n is the number of repeating units on polyethylene glycol, and the molecular weight of PEG is Mn=10000, so n=113.

[0025] The polyrotaxane is used in gel materials, elastomeric materials, battery adhesives, solid electrolytes, and biomedical materials.

[0026] Beneficial effects: Compared with the prior art, the present invention has the following advantages:

[0027] 1) Based on the competition mechanism between 3-hydroxyadamantane-1-carboxylic acid and polyethylene glycol in the cyclodextrin cavity, the present invention synthesizes a polyrotaxane with a cyclodextrin coverage of 0.5 to 2.5%; by changing the molecular molar ratio of adamantane derivative and cyclodextrin, PR with different cyclodextrin coverages is synthesized, and the cyclodextrin coverage is controllable within a certain range;

[0028] 2) After α-cyclodextrin is dissolved in water, a certain amount of OH-Ada-COOH is added before PEG is added to assemble with the α-cyclodextrin. After PEG is dissolved, part of the α-cyclodextrin forms a host-guest complex with OH-Ada-COOH, and the number of α-cyclodextrins that can be assembled with PEG decreases, thereby achieving the purpose of reducing the coverage of cyclodextrin.

[0029] 3) The present invention proposes a method for synthesizing a high-yield, low-coverage polyrotaxane that is safe, rapid, and controllable. The reaction is carried out at room temperature in an aqueous phase, and the reaction conditions are mild and green and pollution-free. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 The synthetic route of polyethylene glycol diamine PEG-BA and polyrotaxane PR;

[0031] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the polyrotaxane prepared in Example 1;

[0032] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of the polyrotaxane prepared in Example 2;

[0033] Figure 4 is the hydrogen nuclear magnetic resonance spectrum of the polyrotaxane prepared in Example 3;

[0034] Figure 5 is the hydrogen nuclear magnetic resonance spectrum of the polyrotaxane prepared in Example 4;

[0035] Figure 6 is the hydrogen nuclear magnetic resonance spectrum of the polyrotaxane prepared in Example 5;

[0036] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the polyrotaxane prepared in Example 6;

[0037] Figure 8 is the hydrogen nuclear magnetic resonance spectrum of the polyrotaxane prepared in Example 7;

[0038] Fig. 9 Graph showing the relationship between the number of CDs on a single PEG chain and the CD / OH-Ada-COOH concentration ratio in Examples 1-7. DETAILED DESCRIPTION

[0039] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described below in conjunction with specific embodiments. In the following examples, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art. If specific conditions are not specified in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. If the manufacturer is not specified for the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0040] In the following examples, α-CD is α-cyclodextrin, PEG is polyethylene glycol, CDI is N,N'-carbonyldiimidazole, EDA is ethylenediamine, OH-Ada-COOH is 3-hydroxyadamantane-1-carboxylic acid, PEG-BA is polyethylene glycol diamine, and DMT-MM is 4-(4,6-dimethoxytriazine-2-yl)-4-methylmorpholine hydrochloride.

[0041] Figure 1 The synthetic route of polyethylene glycol diamine PEG-BA and polyrotaxane PR is as follows:

[0042] 1) Place a certain amount of PEG monomer in a three-necked flask and dry overnight to remove moisture from the system; add an organic solvent under the protection of an inert gas to dissolve the PEG monomer, then add the formula amount of CDI, add a small amount of EDA after a period of reaction, add ether to precipitate, filter and dry to obtain PEG-BA;

[0043] 2) Dissolve α-CD in a solvent, add a small amount of OH-Ada-COOH after it is completely dissolved, stir until dissolved, add the formulated amount of PEG-BA, continue stirring until the transparency of the system decreases, and refrigerate to obtain a pseudopolyrotaxane;

[0044] 3) The formulated amount of OH-Ada-COOH and DMT-MM is dissolved in a solvent and then added to the pseudopolyrotaxane. After a period of reaction, a small amount of DMT-MM is added. After the water is removed by rotary evaporation, a certain amount of DMSO is added to make the white solid transparent. The system is transferred to a dialysis tape for dialyzing, and then freeze-dried to obtain a polyrotaxane with controllable cyclodextrin coverage.

[0045] Example 1

[0046] A method for preparing a polyrotaxane with controllable cyclodextrin coverage, specifically comprising the following steps:

[0047] 1) Weigh 10 g of PEG (1 mmol, Mn = 10000) into a 250 mL three-necked bottle, dry in an oven at 85 °C overnight to remove moisture from the system, add 25 mL of anhydrous THF under argon atmosphere, and stir at 50 °C until PEG is dissolved;

[0048] 2) adding 0.85 g of CDI to the system obtained in step 1) through a solid funnel, reacting at 50° C. for 24 h, and after the reaction, adding 1 mL of EDA dropwise, and continuing to react at 50° C. for 24 h to obtain a reaction solution; adding the obtained reaction solution dropwise to a large amount of ether, filtering to obtain a white precipitate, dissolving the precipitate with a small amount of dichloromethane, and then adding dropwise to a large amount of ether again, filtering the precipitate to obtain a white powdery solid, and drying in an oven at 85° C. overnight to obtain PEG-BA;

[0049] 3) Weigh 5.0g α-CD and dissolve it in 35mL deionized water. After it is completely dissolved, add 0.05g OH-Ada-COOH and stir until it is completely dissolved. The solution is clear and transparent. Add 1.0g PEG-BA and stir until it is dissolved. A white precipitate begins to form. As the stirring time increases, the transparency of the system decreases. After stirring until the transparency of the system decreases, refrigerate and assemble at 4°C for 24h to obtain a pseudopolyrotaxane.

[0050] 4) 0.6 g OH-Ada-COOH and 1.2 g DMT-MM were dissolved in 12 mL deionized water, and the pseudopolyrotaxane obtained in step 3) was added. After mechanical stirring at room temperature for 24 h, 0.6 g DMTMM was added and the reaction was continued for 12 h. After rotary evaporation to remove water in the system, 20 mL DMSO was added to turn the white solid into a transparent liquid, indicating complete disassembly;

[0051] 5) The transparent liquid obtained in step 4) was dialyzed in 4000 mL of deionized water for two days using a pre-treated dialysis bag (MWCO: 12000) to remove unreacted small molecules, and the water was changed 5-6 times, followed by freeze-drying to obtain a cyclodextrin-covered polyrotaxane with a yield of 15-22%.

[0052] Example 2

[0053] When preparing polyrotaxane with controllable cyclodextrin coverage, the mass of OH-Ada-COOH added in step 3) is 0.1 g, and the remaining preparation methods and parameters are the same as those in Example 1. The yield of polyrotaxane covered with cyclodextrin is 20-23%.

[0054] Example 3

[0055] When preparing a polyrotaxane with controllable cyclodextrin coverage, the mass of OH-Ada-COOH added in step 3) is 0.3 g, and the remaining preparation methods and parameters are the same as those in Example 1. The yield of the obtained polyrotaxane is 14-20%.

[0056] Example 4

[0057] When preparing polyrotaxane with controllable cyclodextrin coverage, the mass of OH-Ada-COOH added in step 3) is 0.72 g, and the remaining preparation methods and parameters are the same as those in Example 1. The yield of the obtained polyrotaxane is 17-26%.

[0058] Example 5

[0059] When preparing a polyrotaxane with controllable cyclodextrin coverage, the refrigerated assembly time in step 3) is 48 hours, and the remaining preparation methods and parameters are the same as those in Example 1. The yield of the obtained polyrotaxane is 19-25%.

[0060] Example 6

[0061] When preparing polyrotaxane with controllable cyclodextrin coverage, the refrigerated assembly time in step 3) is 48 hours, and the remaining preparation methods and parameters are the same as those in Example 2. The yield of the obtained polyrotaxane is 16-21%.

[0062] Example 7

[0063] When preparing polyrotaxane with controllable cyclodextrin coverage, the refrigerated assembly time in step 3) is 48 hours, and the remaining preparation methods and parameters are the same as those in Example 3. The yield of the obtained polyrotaxane is 18-24%.

[0064] Comparative Example 1

[0065] 1) Synthesis of PEG-BA:

[0066] Weigh 10 g of PEG (1 mmol, Mn = 10000) into a 250 mL three-necked bottle, dry in an oven at 85 ° C overnight to remove moisture from the system, add 25 mL of anhydrous THF under argon atmosphere, and stir at 50 ° C until PEG is dissolved; add 0.85 g of CDI to the obtained system through a solid funnel, react at 50 ° C for 24 h, add 1 mL of EDA dropwise after the reaction, and continue to react at 50 ° C for 24 h to obtain a reaction solution; add the obtained reaction solution dropwise to a large amount of ether, filter to obtain a white precipitate, use a small amount of dichloromethane to dissolve the precipitate, and then add it dropwise to a large amount of ether again, precipitate and filter to obtain a white powdery solid, dry it in an oven at 85 ° C overnight to obtain PEG-BA;

[0067] 2) PEG-BA and hydroxypropylated α-cyclodextrin assemble to form pseudopolyrotaxane:

[0068] Weigh 0.7680g HPCD and dissolve it in 5mL deionized water. After it is completely dissolved, add 0.2214g PEG-BA and stir until it is completely dissolved. The solution remains clear and transparent. Put it in a 4℃ refrigerator for 48 hours. After taking it out, it is still a clear and transparent solution.

[0069] 3) End-capping reaction of pseudopolyrotaxane:

[0070] Weigh 0.15g OH-Ada-COOH and 0.33g DMT-MM and add them to the above system, stir with a magnetic stirrer at room temperature, and react for 24 hours. After adding OH-Ada-COOH, the system changes from clear and transparent to light yellow turbid. Transfer the reaction solution to a pretreated dialysis bag (MWCO: 12000), dialyze in deionized water for two days, and change the water 5-6 times until the liquid in the dialysis bag becomes clear and transparent. Freeze-dry to obtain a white powder product with a yield of 20-27%.

[0071] Example 8

[0072] The polyrotaxanes covered with cyclodextrin in Examples 1-7 and Comparative Example 1 were characterized by NMR, and the number of α-CDs generated in PR was calculated by the integral area of ​​H on α-CD and the integral ratio of H on the methylene group of PEG backbone. The results are shown in Table 1 below, where N CD / per PEG represents the number of PEG chains passing through α-cyclodextrin; CD coverage / % represents the coverage rate of cyclodextrin. The H NMR spectra of the polyrotaxane prepared in Example 1-7 are shown in FIG. Figure 2-8 shown.

[0073] Table 1 Cyclodextrin coverage results of polyrotaxanes prepared in Examples 1-7 and Comparative Example 1

[0074] <![CDATA[N CD / per PEG]]> CD coverage / % Example 1 1.5 1.3 Example 2 0.8 0.7 Example 3 0.7 0.6 Example 4 0.5 0.5 Example 5 13 1.5 Example 6 3.2 2.5 Example 7 1.7 1.5 Comparative Example 1 1.6 1.4

[0075] From Table 1 and Fig. 9 It can be seen that shortening the assembly time and increasing the OH-Ada-COOH can reduce the coverage of α-CD on the PEG chain. When the concentration ratio of α-CD and OH-Ada-COOH is fixed, the number of α-CD on a single PEG chain increases as the cold storage assembly time increases from 24 hours to 48 hours. When the cold storage assembly time is 24 hours, the number of α-CD does not increase significantly with the increase of the concentration ratio of α-CD and OH-Ada-COOH. When the cold storage assembly time is 48 hours, the coverage of α-CD increases with the increase of the concentration ratio of the two. When the cold storage time is 24 hours, due to the presence of OH-Ada-COOH in the α-CD cavity, PEG-BA is difficult to assemble with α-CD to form a polyrotaxane. When the cold storage time is extended to 48 hours, as the ratio of OH-Ada-COOH decreases, PEG-BA can assemble with more α-CD, and the coverage of the resulting polyrotaxane α-CD increases. When the α-CD coverage is low, the synthesized polyrotaxane is water-soluble. When the number of α-CDs is 13, the synthesized polyrotaxane will form a white precipitate in water.

[0076] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A method for preparing a polyrotaxane with controllable cyclodextrin coverage, characterized in that: α-cyclodextrin, 3-hydroxyadamantane-1-carboxylic acid and polyethylene glycol diamine are dissolved in deionized water and refrigerated to assemble to form a pseudopolyrotaxane, which is then capped to obtain a polyrotaxane; wherein the polyethylene glycol diamine is prepared from polyethylene glycol and N,N'-carbonyldiimidazole, and the cyclodextrin coverage of the polyrotaxane is directional regulated by regulating the mass ratio of α-cyclodextrin and 3-hydroxyadamantane-1-carboxylic acid, the order of adding 3-hydroxyadamantane-1-carboxylic acid, and the refrigerated assembly time.

2. The method for preparing a polyrotaxane with controllable cyclodextrin coverage according to claim 1, characterized in that: The preparation process of the polyethylene glycol diamine is as follows: under the protection of an inert gas, polyethylene glycol is dissolved in anhydrous tetrahydrofuran, N,N'-carbonyldiimidazole and ethylenediamine are added, and drying is performed after the reaction is completed to obtain the polyethylene glycol diamine.

3. The method for preparing a polyrotaxane with controllable cyclodextrin coverage according to claim 1, characterized in that: The mass ratio of the α-cyclodextrin, 3-hydroxyadamantane-1-carboxylic acid and polyethylene glycol diamine is 100:14.4 to 1:

20.

4. The method for preparing a polyrotaxane with controllable cyclodextrin coverage according to claim 1, characterized in that: The temperature of the refrigerated assembly is 4° C., and the time of the refrigerated assembly is 24 hours or 48 hours.

5. The method for preparing a polyrotaxane with controllable cyclodextrin coverage according to claim 1, characterized in that: The order of adding the 3-hydroxyadamantane-1-carboxylic acid is: first add 3-hydroxyadamantane-1-carboxylic acid and α-cyclodextrin for pre-assembly, then add polyethylene glycol diamine for refrigerated assembly, and then add 3-hydroxyadamantane-1-carboxylic acid for end-capping reaction after preparing the pseudo-polyalkane.

6. The method for preparing a polyrotaxane with controllable cyclodextrin coverage according to claim 5, characterized in that: The mass ratio of 3-hydroxyadamantane-1-carboxylic acid added in the pre-assembly to 3-hydroxyadamantane-1-carboxylic acid added in the end-capping reaction is 1 to 14.4:

12.

7. The method for preparing a polyrotaxane with controllable cyclodextrin coverage according to claim 1, characterized in that: The specific steps include: 1) Under the protection of inert gas, polyethylene glycol is dissolved in anhydrous tetrahydrofuran, N,N'-carbonyldiimidazole is first added to react, and ethylenediamine is added dropwise to react after the reaction is completed to obtain a reaction liquid; the obtained reaction liquid is added dropwise to ether, filtered, and the precipitate is dissolved with dichloromethane, and then added dropwise to ether again, the precipitate is filtered, and dried to obtain polyethylene glycol diamine; 2) dissolving α-cyclodextrin in deionized water, adding 3-hydroxyadamantane-1-carboxylic acid after it is completely dissolved, stirring until it is completely dissolved, adding the polyethylene glycol diamine prepared in step 1), stirring until the transparency of the system decreases, and refrigerating and assembling to prepare a pseudopolyrotaxane; 3) dissolving 3-hydroxyadamantane-1-carboxylic acid and 4-(4,6-dimethoxytriazine-2-yl)-4-methylmorpholine hydrochloride in deionized water, adding the pseudopolyrotaxane obtained in step 2) above, mechanically stirring at room temperature for 24 hours, then adding 4-(4,6-dimethoxytriazine-2-yl)-4-methylmorpholine hydrochloride, continuing the reaction for 12 hours, removing water in the system by rotary evaporation, and adding dimethyl sulfoxide to obtain a transparent liquid; 4) The transparent liquid obtained in step 3) is dialyzed in deionized water for two days using a dialysis bag, the water is changed 5-6 times, and freeze-dried to obtain a cyclodextrin-covered polyrotaxane.

8. The method for preparing a polyrotaxane with controllable cyclodextrin coverage according to any one of claims 1 to 7, wherein the polyrotaxane is prepared.

9. The polyrotaxane according to claim 8, characterized in that The structural formula is as follows: Among them, n=113.

10. Use of the polyrotaxane according to claim 8 or 9 in gel materials, elastomeric materials, battery adhesives, solid electrolytes, and biopharmaceutical materials.

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