A preparation method of a supramolecular polymer gel based on reaction of pillar[5]arene and crown ether

Abstract

The application discloses a preparation method of a supramolecular polymer gel based on column [5] arene and crown ether reaction, and different supramolecular polymer materials are constructed based on P5-TPN and B21C7-TAS two kinds of host-guest interactions through monomers LP-A, LP-B, EF, C and D. Supramolecular polymer network structures include SPN-EF-1-5, SPN-AC-1-5 and SPN-BD-1-5. The specific operation is as follows: SPN-EF-1-5 is constructed through monomers LP-A, LP-B and EF; SPN-AC-1-5 is constructed through monomers LP-A and C; and SPN-BD-1-5 is constructed through monomers LP-B and D. The preparation method of each SPN material is that LP-A / LP-B is dissolved in 3ml of DCM, then a certain amount of EF / C / D is added into the above solution as a crosslinking agent, and corresponding SPN is obtained.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of chemistry, and particularly relates to a preparation method of a supramolecular polymer gel constructed based on a reaction of a pillar[5]arene and a crown ether. BACKGROUND

[0002] Supramolecular polymer networks are networks formed by polymers connected to each other through reversible non-covalent bonds, and they have good stimulus responsiveness, self-repairing, and shape memory performance, and other performances that traditional materials do not have, and thus have attracted more and more attention.

[0003] Supramolecular polymer gels represent a brand new concept and a more complex gel system. The construction of this new supramolecular system is based on the multi-level assembly of multiple non-covalent interactions. That is, small molecule building blocks are first assembled into supramolecular polymers, and the multi-level assembly of these non-covalent polymers forms the nanostructure of the gel. Supramolecular polymer gels have many brand new characteristics in terms of structure and performance. Therefore, although the research on supramolecular polymer gels has been carried out for a very short time, the unique nature and great potential of this system have attracted more and more attention from scientists.

[0004] In view of the above factors, the application provides a preparation method of a supramolecular polymer gel constructed based on a reaction of a pillar[5]arene and a crown ether. The supramolecular polymer gel is successfully constructed by using the double host-guest reaction of the pillar[5]arene on two different monomers and the crown ether. The gel has responsiveness to competitive guests and potassium ions. The mechanical performance research on the supramolecular polymer gel shows that the gel has excellent mechanical performance. SUMMARY

[0005] The application aims to provide a preparation method of a supramolecular polymer gel constructed based on a reaction of a pillar[5]arene and a crown ether, so as to solve the problems in the background.

[0006] The application is achieved by the following technical scheme: a preparation method of a supramolecular polymer gel constructed based on a reaction of a pillar[5]arene and a crown ether, comprising the following steps:

[0007] Different supramolecular polymer materials are constructed based on the P5-TPN and B21C7-TAS two kinds of host-guest interactions through the monomers LP-A, LP-B, EF, C, and D. The supramolecular polymer network structure includes SPN-EF-1-5, SPN-AC-1-5, and SPN-BD-1-5.

[0008] The specific operation is as follows:

[0009] SPN-EF-1-5 is constructed by monomer LP-A, LP-B, EF; SPN-AC-1-5 is constructed by monomer LP-A, C; SPN-BD-1-5 is constructed by monomer LP-B, D; the preparation method of each SPN material is that LP-A / LP-B is dissolved in 3ml of DCM, then a certain amount of EF / C / D is added as a crosslinking agent in the above solution to obtain the corresponding SPN;

[0010] The chemical structure of EF is as follows:

[0011]

[0012] The chemical structure of C is as follows:

[0013]

[0014] The chemical structure of D is as follows:

[0015]

[0016] Further, the molar ratio of monomer LP-A, LP-B and crosslinking agent EF in the SPN-EF-1-5 is 5:5:1, 5:5:2, 5:5:3, 5:5:4 or 5:5:5 respectively.

[0017] Further, the molar ratio of monomer LP-A and crosslinking agent C in the SPN-AC-1-5 is 10:1, 10:2, 10:3, 10:4 or 10:5 respectively.

[0018] Further, the molar ratio of monomer LP-B and crosslinking agent D in the SPN-BD-1-5 is 10:1, 10:2, 10:3, 10:4 or 10:5 respectively.

[0019] Further, the synthesis of compound LP-A includes the following steps: taking compound A (2.00g, 1.8mmol), compound 1 (2.59g, 8.78mmol), placing in a three-necked flask, adding heavy boiling tetrahydrofuran for dissolution; placing Ru catalyst (0.30, 0.35mmol) in a constant pressure burette, dissolving in heavy boiling tetrahydrofuran; after three times of N2 flushing, the catalyst is slowly dropped into the three-necked flask, stirred at room temperature for 24h, after the reaction is completed, 0.1mL of pure vinyl ether is added for quenching, after stirring for 60 minutes, the mixture is dropped into 400mL of rapidly stirred methanol, immediately forming a light gray precipitate, the solid is vacuum dried for 24h to obtain the target polymer (3.88g, 83.65%);

[0020] The structure of Ru catalyst is as follows:

[0021]

[0022] Further, the synthesis of monomer LP-A includes the following steps: cis-5-norbornene- exo-2,3-dicarboxylic anhydride is used as a starting material, and is reacted with n-butanol and 11-aminoundecanoic acid respectively to generate compound 1 and compound 2. Compound A is generated by reacting compound 3 with compound 1, and the obtained compound A and compound 1 are fed in a molar ratio of 1:5, and olefin metathesis is generated under the action of a Ru catalyst to obtain monomer LP-A (LP-A, Mn = 54 kDa);

[0023] The synthesis path of monomer LP-A is as follows:

[0024]

[0025] Further, the synthesis of compound LP-B includes the following steps: compound B (1.00 g, 1.6 mmol) and compound 1 (2.33 g, 7.9 mmol) are placed in a three-necked flask, and are dissolved in redistilled tetrahydrofuran; the Ru catalyst (0.27, 0.31 mmol) is placed in a constant-pressure burette, and is dissolved in redistilled tetrahydrofuran; after N2 is pumped three times, the catalyst is slowly dropped into the three-necked flask, and is stirred at room temperature for 24 h; after the reaction is completed, 0.1 mL of pure vinyl ether is added for quenching, and after stirring for 60 min, the mixture is dropped into 400 mL of rapidly stirred methanol, and a light gray precipitate is immediately formed; the solid is vacuum-dried for 24 h to obtain the target polymer (2.74 g, 81.32%);

[0026] Further, the synthesis of monomer LP-B includes the following steps: cis-5-norbornene- exo-2,3-dicarboxylic anhydride and 5-amino-1-pentanol are used as starting materials to generate compound 4. Compound B is generated by reacting compound 4 with compound 5, and the obtained compound B and compound 1 are fed in a molar ratio of 1:5, and olefin metathesis is generated under the action of a Ru catalyst to obtain monomer LP-B (LP-B, Mn = 36 kDa);

[0027] The synthesis path of monomer LP-B is as follows:

[0028]

[0029] The synthesis path of compound B is as follows:

[0030]

[0031] Compared with the prior art, the present application has the following beneficial effects:

[0032] The present application utilizes the double host-guest reaction of column [5] arene on two different monomers and crown ether to successfully construct a supramolecular polymer gel, which has responsiveness to competitive guests, potassium ions and the like, and the mechanical property research of the formed supramolecular polymer gel shows that the gel has excellent mechanical property, and the gel is applied to the field of stimulus-responsive materials. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 It is a hydrogen spectrum diagram of compound LP-A in deuterated chloroform;

[0034] Figure 2 (a) GPC elution curve of compound LP-A with THF as eluent, (b) schematic diagram of molecular weight distribution curve;

[0035] Figure 3 It is a hydrogen spectrum diagram of compound LP-B in deuterated chloroform;

[0036] Figure 4 (a) GPC elution curve of compound LP-B with THF as eluent, (b) schematic diagram of molecular weight distribution curve;

[0037] Figure 5 It is a nuclear magnetic resonance hydrogen spectrum (400MHz, deuterated chloroform and deuterated acetone (3:1, v / v), 298K): (a) EF, (b) LP-B, (c) LP-A, (d) LP-A+LP-B+EF, complexed protons are subscripted as c, and uncomplexed are uc;

[0038] Figure 6 It is a nuclear magnetic resonance hydrogen spectrum (400MHz, deuterated chloroform and deuterated acetone (3:1, v / v), 298K): (a) C, (b) LP-A, (c) LP-A+C, complexed protons are subscripted as c, and uncomplexed are uc;

[0039] Figure 7 It is a nuclear magnetic resonance hydrogen spectrum (400MHz, deuterated chloroform and deuterated acetone (3:1, v / v), 298K): (a) D, (b) LP-B, (c) LP-B+D, complexed protons are subscripted as c, and uncomplexed are uc;

[0040] Figure 8 It is a schematic diagram of gel-sol changes based on different stimuli of SPN-EF system;

[0041] Figure 9 It is a schematic diagram of gel to sol changes of (a) SPN-CD system adding butanedinitrile, (b) SPN-BD system based on K + gel-sol reversible changes schematic diagram;

[0042] Figure 10(a) Stress-strain curves of the SPN-EF system, (b) Young's modulus and toughness of the SPN-EF system, (c) Stress-strain curves of SPN-EF5, SPN-AC1 and SPN-BD5, (d) Comparison of mechanical properties.

[0043] Figure 11 (a) Stress-strain curves of the SPN-AC system, (b) Stress-strain curves of the SPN-BD system.

[0044] (c) Young's modulus and toughness of the SPN-AC system; (b) Young's modulus and toughness of the SPN-BD system.

[0045] Figure 12 (a) Thermogravimetric analysis of SPN-EF5 (heating rate 10℃ / min), (b) Differential thermal analysis of SPN-EF5. Detailed Implementation

[0046] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0047] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "joining" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0048] In the description of this invention, it should be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention. Specific Implementation Example 1:

[0050] like Figures 1-12 As shown, a method for preparing supramolecular polymer gel based on the reaction of columnar aromatic hydrocarbons and crown ethers includes the following steps;

[0051] Different supramolecular polymer materials are constructed by monomers LP-A, LP-B, EF, C and D based on two kinds of host-guest interactions of P5-TPN and B21C7-TAS, and the supramolecular polymer network structures include SPN-EF-1-5, SPN-AC-1-5 and SPN-BD-1-5.

[0052] The specific operation is as follows:

[0053] SPN-EF-1-5 is constructed by monomers LP-A, LP-B and EF; SPN-AC-1-5 is constructed by monomers LP-A and C; and SPN-BD-1-5 is constructed by monomers LP-B and D. The preparation method of each SPN material is as follows: LP-A / LP-B is dissolved in 3 ml of DCM, then a certain amount of EF / C / D is added as a crosslinking agent in the above solution to obtain the corresponding SPN.

[0054] The chemical structure of EF is as follows:

[0055]

[0056] The chemical structure of C is as follows:

[0057]

[0058] The chemical structure of D is as follows:

[0059]

[0060] The molar ratio of monomers LP-A, LP-B and crosslinking agent EF in the SPN-EF-1-5 is 5:5:1, 5:5:2, 5:5:3, 5:5:4 or 5:5:5, respectively.

[0061] The molar ratio of monomers LP-A and crosslinking agent C in the SPN-AC-1-5 is 10:1, 10:2, 10:3, 10:4 or 10:5, respectively.

[0062] The molar ratio of monomers LP-B and crosslinking agent D in the SPN-BD-1-5 is 10:1, 10:2, 10:3, 10:4 or 10:5, respectively. Specific embodiment two:

[0064] The synthesis of compound LP-A includes the following steps: taking compound A (2.00 g, 1.8 mmol), compound 1 (2.59 g, 8.78 mmol), placing in a three-necked flask, and dissolving by adding heavy tetrahydrofuran; placing Ru catalyst (0.30, 0.35 mmol) in a constant pressure burette, dissolving by adding heavy tetrahydrofuran; after three times of N2 flushing, slowly dropping the catalyst into the three-necked flask, stirring at room temperature for 24 h, adding 0.1 mL of pure vinyl ether to quench after the reaction is completed, stirring for another 60 min, and then dropping the mixture into 400 mL of rapidly stirred methanol to immediately form light gray precipitates; and vacuum drying the solid for 24 h to obtain the target polymer (3.88 g, 83.65%);

[0065] The structure of the Ru catalyst is as follows:

[0066]

[0067] The synthesis of monomer LP-A includes the following steps: taking cis-5-norbornene-endo-2,3-dicarboxylic anhydride as a starting material, respectively reacting with n-butanol and 11-aminoundecanoic acid to generate compound 1 and compound 2. Compound 3 is reacted with compound 1 to generate compound A, and the obtained compound A and compound 1 are fed in a molar ratio of 1:5 to undergo olefin metathesis under the action of a Ru catalyst to obtain monomer LP-A (LP-A, Mn=54 kDa);

[0068] The synthesis path of monomer LP-A is as follows:

[0069] Specific embodiment three:

[0071] The synthesis of compound LP-B includes the following steps: taking compound B (1.00 g, 1.6 mmol), compound 1 (2.33 g, 7.9 mmol), placing in a three-necked flask, and dissolving by adding heavy tetrahydrofuran; placing Ru catalyst (0.27, 0.31 mmol) in a constant pressure burette, dissolving by adding heavy tetrahydrofuran; after three times of N2 flushing, slowly dropping the catalyst into the three-necked flask, stirring at room temperature for 24 h, adding 0.1 mL of pure vinyl ether to quench after the reaction is completed, stirring for another 60 min, and then dropping the mixture into 400 mL of rapidly stirred methanol to immediately form light gray precipitates; and vacuum drying the solid for 24 h to obtain the target polymer (2.74 g, 81.32%);

[0072] The synthesis of monomer LP-B includes the following steps: starting with cis-5-norbornene-ex-2,3-dicarboxylic anhydride and 5-amino-1-pentanol as starting materials to generate compound 4. Compound 4 reacts with compound 5 to generate compound B. Compound B and compound 1 are then fed at a molar ratio of 1:5 and subjected to an olefin metathesis reaction in the presence of a Ru catalyst to obtain monomer LP-B (LP-B, Mn = 36 kDa).

[0073] The synthetic route for monomer LP-B is as follows:

[0074]

[0075] The synthetic route of compound B is as follows:

[0076]

[0077] Three supramolecular polymer networks (SPNs) were constructed based on the host-guest interactions of B21C7-TAS and P5-TAPN. SPN-EF was constructed using monomers LP-A, LP-B, and EF; SPN-AC was constructed using monomers LP-A and C; and SPN-BD was constructed using monomers LP-B and D. The preparation method for each SPN material involved dissolving LP-A / LP-B in 3 ml of DCM, and then adding a measured amount of EF / C / D as crosslinking agents to the solution to obtain the corresponding SPN.

[0078] The molar ratios of monomers LP-A and LP-B and crosslinking agent EF in SPN-EF-1-5 are 5:5 / 1, 5:5:2, 5:5:3, 5:5:4, or 5:5:5 (B21C7 fragment / P5 fragment / crosslinking agent).

[0079] The molar ratio of monomer LP-A and crosslinking agent C in SPN-AC-1-5 is 10:1, 10:2, 10:3, 10:4 or 10:5 (P5 fragment / crosslinking agent).

[0080] The molar ratio of monomer LP-B and crosslinking agent D in SPN-BD-1-5 was 10:1, 10:2, 10:3, 10:4, or 10:5 (B21C7 fragment / crosslinking agent). After mixing and stirring for 2 hours, the solvent was evaporated at 40°C, and the sample was vacuum stored at 60°C for 24 hours.

[0081] To obtain samples for various tests, the corresponding SPNs were obtained by hot-pressing them in a mold at 80°C for 10 minutes. The self-assembly process of monomers in solution to form SPNs was investigated. Monomers LP-A, LP-B, and EF formed complex proton NMR spectra in a deuterated chloroform / deuterated acetone mixed solvent (3:1, v / v). Figure 5 ).exist Figure 5In monomer EF, the chemical shifts of hydrogen protons F1 and F2 shift significantly to higher fields, while in monomer LP-B, the proton L... B8 The hydrogen protons E1-E4 on monomer EF showed a clear shift towards higher fields, consistent with model experimental results, indicating that the monomers self-assembled to form SPNs. Monomers LP-A+D and LP-B+C also formed complex proton spectra in mixed solvents. Figures 6-7 ).exist Figure 6 In the monomer C, the C1-C4 chemical shifts of hydrogen protons shift significantly to higher fields, indicating that the neutral guest TPN enters the cavity of the column[5] aromatic hydrocarbon; Figure 7 In the study, the chemical shifts of hydrogen protons D1 and D2 in monomer D significantly shifted to higher fields and split into two sets of signal peaks, indicating that host-guest recognition occurred between B21C7 and TAS. This result is consistent with the LP-A+LP-B+EF results, suggesting that LP-A+C and LP-B+D formed two SPNs through the host-guest interactions of TPN-P5 and TAS-B21C7.

[0082] When the supramolecular polymer network (SPN) is formed, and the monomer concentration of the SPNs constructed by LP-A+LP-B+EF exceeds 7.5 mM (LP-A = 7.5 mM), the polymer undergoes a sol-to-gel transition. The interconversion of the sample from gel to sol can be achieved through heating / cooling. This is because heating reduces the binding force between the host and guest molecules, promoting the transition from gel to sol; conversely, as the temperature decreases, the binding force recovers, causing the sample to revert to a gel state. Furthermore, by adding or removing K... + Ions can also be used to detect the interconversion of samples from gel to sol. Figure 8 ac). B21C7 and K + The complexing ability of succinic anhydride is greater than that of B21C7 and TAS, consistent with the NMR results. The addition of succinic anhydride can also achieve the transformation of the sample from gel to sol. Furthermore, when the monomer concentration of SPNs constructed with LP-A+C exceeds 20 mM (LP-A = 20 mM) and the monomer concentration of SPNs constructed with LP-B+D exceeds 25 mM (LP-B = 25 mM), the polymers both underwent a sol-to-gel transformation. Moreover, the addition of succinic anhydride to LP-A+C can also achieve the transformation of the sample from gel to sol. Figure 9 a) In LP-B+D, K is added or removed. + Ions can also be used to detect the interconversion of samples from gel to sol. Figure 9 b).

[0083] To verify the mechanical properties of the supramolecular polymer network structure constructed based on the interactions of TPN-P5 and TAS-B21C7, tensile tests were conducted on the obtained supramolecular polymer network block samples using a universal tensile testing machine. First, a tensile test was performed on sample SPN-EF at a deformation rate of 100 mm / min at room temperature to investigate the mechanical properties of the supramolecular polymer network structure constructed under the synergistic effect of the two host-guest interactions. The stress-strain curves, Young's modulus, and calculated toughness values ​​of SPN-EF-1-5 are shown below. Figure 10 As shown in ab, besides the maximum strain, the overall mechanical properties of SPN gradually improved with increasing crosslinking agent content. Young's modulus increased from 2.48 MPa (SPN-EF-1) to 30.29 MPa (SPN-EF-5), and toughness increased from 20.92 MJ m⁻³ (SPN-EF-1) to 41.98 MJ m⁻³ (SPN-EF-5). These results reveal that the crosslinking density of the supramolecular polymer network structure built based on the interactions of TPN-P5 and TAS-B21C7 plays a crucial role in determining the mechanical properties of SPN. Overall, SPN-EF-5 exhibits balanced and comprehensive mechanical properties, and therefore was selected as the representative sample for subsequent studies.

[0084] To further investigate the mechanical properties of supramolecular polymer network structures constructed under the synergistic effect of TPN-P5 and TAS-B21C7 host-guest interactions, and to compare the differences in mechanical properties of supramolecular polymer structures formed by the individual and combined effects of these two interactions, two control groups were designed and synthesized. Control group one was the supramolecular polymer network SPN-AC constructed based solely on the TPN-P5 host-guest interaction; control group two was the supramolecular polymer network SPN-BD constructed based solely on the TAS-B21C7 host-guest interaction. The stress-strain curve, Young's modulus, and calculated toughness values ​​of SPN-AC-1-5 are shown in Figure 1. Figure 11 As shown in Figure ac, the results are the opposite of those for the SPN-EF system. With increasing crosslinking degree, the Young's modulus decreases from 135.48 MPa (SPN-EF-1) to 11.82 MPa (SPN-EF-5), and the toughness decreases from 26.40 MJ m⁻³ (SPN-EF-1) to 17.34 MJ m⁻³ (SPN-EF-5). The maximum strain increases with increasing crosslinking degree. The stress-strain curves, calculated Young's modulus, and toughness of SPN-BD-1-5 are shown below. Figure 12b. In addition to the maximum strain, with the increase of crosslinking agent content, the overall mechanical properties of SPN gradually improved, the Young's modulus increased from 0.89 MPa (SPN-EF-1) to 19.86 MPa (SPN-EF-5), and the toughness increased from 9.62 MJ m-3 (SPN-EF-1) to 12.70 MJ m-3 (SPN-EF-5). It can be known that SPN-AC1 has the optimal performance in the SPN-AC system, SPN-BD5 has the optimal mechanical properties in the SPN-BD system, and SPN-EF5 has the optimal mechanical properties in the SPN-EF system. As shown in Figure 10 c-d. Compared with SPN-EF5, it can be seen that SPN-EF5 is obviously superior to the control in the mechanical properties except the Young's modulus, and it is determined that the supramolecular polymer based on TPN-P5, TAS-B21 C7 two kinds of host-guest interactions, the mechanical properties of the supramolecular polymer network constructed by two kinds of host-guest interactions are better than that of the supramolecular polymer constructed by one kind of host-guest interaction.

[0085] The thermal stability of SPN-EF5 was studied, and the thermal stability of the supramolecular polymer network was studied by thermogravimetric analysis (TGA). As shown in Figure 12 (a). The thermal decomposition before 319°C is almost negligible, and when the temperature increases from 319°C to 528°C, the weight loss of the polymer thermal decomposition is from 2.6% to 79.5%. These weight losses are due to the decomposition of pillar five and crown ether derivatives in the supramolecular polymer network. Differential thermal analysis further proves the thermal stability of the supramolecular polymer network 12(b). In the range of 30-250°C, the DSC curve has no obvious peak, indicating that no obvious thermal decomposition occurs below 250°C, which is consistent with the results of thermogravimetric analysis.

[0086] The above-mentioned monomers LP-A, LP-B, EF, C, D, based on P5-TPN, B21C7-TAS two kinds of host-guest interactions, constructed three kinds of supramolecular polymer network structures—SPN-EF, SPN-AC, SPN-BD. Through the above-mentioned SPN system characterization means, it is proved that the supramolecular polymer is successfully constructed. The influence of the formed supramolecular polymer on the stimulus is studied, at the same time, the gel pair formed after the polymer concentration exceeds a certain limit has a response to temperature, K + and other factors. In addition, the mechanical properties of the formed supramolecular polymer network are also studied, and the performance of SPN-EF5 is the best.

[0087] It will be obvious to a person skilled in the art that the application is not limited to the details of the foregoing exemplary embodiments and can be implemented in other concrete forms without departing from the spirit or essential characteristics of the application. The embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. No reference signs in the claims should be considered as limiting the scope of the claims to the identity of the reference signs therein.

[0088] Furthermore, it should be understood that although the description is made on the basis of the embodiments, not every embodiment contains only one independent technical solution, and the description of the specification is only for the sake of clarity, and those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that those skilled in the art can understand.

Claims

1. A method for preparing supramolecular polymer gels based on the reaction of columnar aromatics with crown ethers [5], characterized in that: Comprising the following steps; Different supramolecular polymer materials are constructed by monomers LP-A, LP-B, EF, C, D based on two kinds of host-guest interactions of P5-TPN and B21C7-TAS, and the supramolecular polymer network structure is SPN-EF-1-5; The specific operation is as follows: SPN-EF-1-5 is constructed by monomers LP-A, LP-B and EF; the preparation method of the SPN material is that LP-A / LP-B is dissolved in 3 ml of DCM, then a certain amount of EF / C / D is added as a crosslinking agent to the above solution to obtain the corresponding SPN; The chemical structure of EF is as follows: ； The chemical structure of C is as follows: ; The chemical structure of D is as follows: ； The synthesis of monomer LP-A comprises the following steps: cis-5-norbornene-endo-2,3-dicarboxylic anhydride is used as a starting material, and is reacted with n-butanol and 11-aminoundecanoic acid to generate compound 1 and compound 2 respectively, compound A is generated by the reaction of compound 3 and compound 2, compound A and compound 1 are fed in a molar ratio of 1:5, and olefin metathesis reaction occurs under the action of Ru catalyst to obtain monomer LP-A, Mn = 54 kDa; The synthesis path of monomer LP-A is as follows: ； The synthesis of monomer LP-B comprises the following steps: cis-5-norbornene-endo-2,3-dicarboxylic anhydride and 5-amino-1-pentanol are used as starting materials to generate compound 4, compound B is generated by the reaction of compound 4 and compound 5, and compound B and compound 1 are fed in a molar ratio of 1:5, and olefin metathesis reaction occurs under the action of Ru catalyst to obtain monomer LP-B, wherein LP-B, Mn = 36 kDa; The synthesis path of monomer LP-B is as follows: ； The synthesis path of compound B is as follows; 。 2. The method for preparing supramolecular polymer gels based on the reaction of pillar[5]arene and crown ether according to claim 1, characterized in that: The molar ratio of monomers LP-A, LP-B and crosslinking agent EF in the SPN-EF-1-5 is 5:5:1, 5:5:2, 5:5:3, 5:5:4 or 5:5:5 respectively.

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