Preparation method for constructing supramolecular polymer gel based on reaction of pillar [5] arene and crown ether

Abstract

The invention discloses a preparation method for constructing supramolecular polymer gel based on reaction of pillar [5] arene and crown ether, different supramolecular polymer materials are constructed based on interaction of two subjects and guests of P5-TPN and B21C7-TAS through monomers LP-A, LP-B, EF, C and D. A supramolecular polymer network structure comprises SPN-EF-1-5, SPN-AC-1-5 and SPN-BD-1-5, the specific operation is as follows: constructing SPN-EF-1-5 through monomers LP-A, LP-B and EF; constructing SPN-AC-1-5 by using monomers LP-A and C; the preparation method of each SPN material comprises the following steps: dissolving LP-A / LP-B in 3ml of DCM (Dichloromethane), and then adding quantitative EF / C / D as a cross-linking agent into the solution to obtain the corresponding SPN.

Description

Technical Field

[0001] The present invention belongs to the field of chemical technology, and in particular relates to a preparation method for constructing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether. Background Art

[0002] Supramolecular polymer networks are a type of network structure formed by polymers interconnected by reversible non-covalent bonds. They have properties that traditional materials do not have, such as good stimulus responsiveness, self-healing, and shape memory properties, and therefore have attracted increasing attention.

[0003] Supramolecular polymer gel represents a completely new concept and a more complex gel system. The construction of this new supramolecular system is based on a 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 gel has many new characteristics both in structure and performance. Therefore, although the research on supramolecular polymer gel has been carried out for a short time, the uniqueness and great potential of this system have attracted more and more attention from scientists.

[0004] In view of the above factors, a preparation method for constructing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether is provided. By utilizing the dual host-guest reaction of pillar[5]arene and crown ether on two different monomers, a supramolecular polymer gel is successfully constructed. The gel is responsive to competing guests, potassium ions, etc., and the mechanical properties study shows that the supramolecular polymer gel has specific superior mechanical properties. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether, so as to solve the problems raised in the above background technology.

[0006] The object of the present invention is achieved through the following technical solution: a preparation method for constructing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether, comprising the following steps;

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

[0008] The specific operations are as follows:

[0009] The monomers LP-A, LP-B, and EF were used to construct SPN-EF-1-5; the monomers LP-A and C were used to construct SPN-AC-1-5; the monomers LP-B and D were used to construct SPN-BD-1-5. The preparation method of each SPN material was to dissolve LP-A / LP-B in 3 ml of DCM, and then add a certain amount of EF / C / D as a cross-linking agent to 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] Furthermore, the molar ratios of the monomers LP-A, LP-B and the crosslinker EF in the SPN-EF-1-5 are 5:5:1, 5:5:2, 5:5:3, 5:5:4 or 5:5:5, respectively.

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

[0018] Furthermore, the molar ratio of the monomer LP-B and the cross-linking 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 (2.00 g, 1.8 mmol) and compound 1 (2.59 g, 8.78 mmol), placing them in a three-necked flask, adding redistilled tetrahydrofuran to dissolve; placing Ru catalyst (0.30, 0.35 mmol) in a constant pressure titration funnel, adding redistilled tetrahydrofuran to dissolve; after pumping N2 gas three times, slowly dripping the catalyst into the three-necked flask, stirring at room temperature for 24 hours, adding 0.1 mL of pure vinyl ethyl ether to quench after the reaction is completed, stirring for another 60 minutes, and then dripping the mixture into 400 mL of rapidly stirred methanol, immediately forming a light gray precipitate, and vacuum drying the solid for 24 hours to obtain the target polymer (3.88 g, 83.65%);

[0020] The Ru catalyst structure is as follows:

[0021]

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

[0023] The synthetic route of monomer LP-A is as follows:

[0024]

[0025] Further, the synthesis of compound LP-B includes the following steps: taking compound B (1.00 g, 1.6 mmol) and compound 1 (2.33 g, 7.9 mmol), placing them in a three-necked flask, adding redistilled tetrahydrofuran to dissolve; placing Ru catalyst (0.27, 0.31 mmol) in a constant pressure titration funnel, adding redistilled tetrahydrofuran to dissolve; after pumping N2 gas three times, slowly dripping the catalyst into the three-necked flask, stirring at room temperature for 24 hours, adding 0.1 mL of pure vinyl ethyl ether to quench after the reaction is completed, stirring for another 60 minutes, and then dripping the mixture into 400 mL of rapidly stirred methanol, immediately forming a light gray precipitate, and vacuum drying the solid for 24 hours 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 react to generate compound 4. Compound 4 is reacted with compound 5 to generate compound B, the obtained compound B and compound 1 are added at a molar ratio of 1:5, and an olefin metathesis reaction is carried out under the action of Ru catalyst to obtain monomer LP-B (LP-B, Mn=36kDa);

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

[0028]

[0029] The synthetic route of compound B is as follows;

[0030]

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

[0032] The present invention utilizes the dual host-guest reaction of pillar[5]arene and crown ether on two different monomers to successfully construct a supramolecular polymer gel. The gel is responsive to competing guests, potassium ions, etc. The mechanical properties research of the formed supramolecular polymer gel shows that the gel has specific and superior mechanical properties. The gel is applied in the field of stimulus-responsive materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 Schematic diagram of the hydrogen spectrum 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 This is a schematic diagram of the hydrogen spectrum 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 H NMR spectra (400 MHz, deuterated chloroform and deuterated acetone (3:1, v / v), 298 K): (a) EF, (b) LP-B, (c) LP-A, (d) LP-A+LP-B+EF, the complexed proton subscript is c, and the uncomplexed is uc;

[0038] Figure 6 H NMR spectra (400 MHz, deuterated chloroform and deuterated acetone (3:1, v / v), 298 K): (a) C, (b) LP-A, (c) LP-A+C, the complexed proton subscript is c, and the uncomplexed is uc;

[0039] Figure 7 H NMR spectra (400 MHz, deuterated chloroform and deuterated acetone (3:1, v / v), 298 K): (a) D, (b) LP-B, (c) LP-B+D, the complexed proton subscript is c, and the uncomplexed is uc;

[0040] Figure 8 Schematic diagram of the gel-sol change of the SPN-EF system based on different stimuli;

[0041] Fig. 9 Schematic diagram of the change from gel to sol after adding succinonitrile to (a) SPN-CD system, and (b) K-based + Schematic diagram of the reversible change of gel-sol;

[0042] Fig.10(a) Stress-strain curve of SPN-EF system, (b) Young's modulus and toughness of SPN-EF system, (c) stress-strain curves of SPN-EF5, SPN-AC1, and SPN-BD5, (d) mechanical properties comparison chart;

[0043] Fig.11 (a) Stress-strain curve of SPN-AC system, (b) Stress-strain curve of 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] Fig.12 (a) Thermogravimetric analysis of SPN-EF5 (heating rate 10℃ / min), (b) differential thermal analysis of SPN-EF5. DETAILED DESCRIPTION

[0046] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0047] In the description of the present invention, it should be noted that, unless otherwise clearly specified and limited, the terms "installed", "connected", and "connected" should be understood in a broad sense, for example, it can be a fixed connection, a detachable connection, or an integral connection; it can be directly connected or indirectly connected through an intermediate medium. For ordinary technicians in this field, the specific meanings of the above terms in the present invention can be understood according to specific circumstances.

[0048] In the description of the present invention, it should be understood that the terms "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside" and "outside" etc., indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as a limitation on the present invention. Specific embodiment one:

[0050] like Figure 1-12 As shown, a preparation method for constructing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether comprises the following steps;

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

[0052] The specific operations are as follows:

[0053] The monomers LP-A, LP-B, and EF were used to construct SPN-EF-1-5; the monomers LP-A and C were used to construct SPN-AC-1-5; the monomers LP-B and D were used to construct SPN-BD-1-5. The preparation method of each SPN material was to dissolve LP-A / LP-B in 3 ml of DCM, and then add a certain amount of EF / C / D as a cross-linking agent to 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 ratios of the monomers LP-A, LP-B and the crosslinking agent EF in the SPN-EF-1-5 are 5:5:1, 5:5:2, 5:5:3, 5:5:4 or 5:5:5 respectively.

[0061] The molar ratio of the monomer LP-A to the 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 the monomer LP-B to the cross-linking agent D in the SPN-BD-1-5 is 10:1, 10:2, 10:3, 10:4 or 10:5 respectively. Specific embodiment 2:

[0064] The synthesis of compound LP-A comprises the following steps: taking compound A (2.00 g, 1.8 mmol) and compound 1 (2.59 g, 8.78 mmol), placing them in a three-necked flask, adding redistilled tetrahydrofuran to dissolve; placing Ru catalyst (0.30, 0.35 mmol) in a constant pressure titration funnel, adding redistilled tetrahydrofuran to dissolve; after pumping N2 gas three times, slowly dripping the catalyst into the three-necked flask, stirring at room temperature for 24 hours, adding 0.1 mL of pure vinyl ethyl ether to quench after the reaction is completed, stirring for another 60 minutes, and then dripping the mixture into 400 mL of rapidly stirred methanol, immediately forming a light gray precipitate, and vacuum drying the solid for 24 hours to obtain the target polymer (3.88 g, 83.65%);

[0065] The Ru catalyst structure is as follows:

[0066]

[0067] 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 to generate compound 1 and compound 2 respectively. Compound 3 is reacted with compound 1 to generate compound A, and the obtained compound A and compound 1 are fed at a molar ratio of 1:5, and an olefin metathesis reaction is carried out under the action of a Ru catalyst to obtain monomer LP-A (LP-A, Mn=54kDa);

[0068] The synthetic route 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) and compound 1 (2.33 g, 7.9 mmol), placing them in a three-necked flask, adding redistilled tetrahydrofuran to dissolve; placing Ru catalyst (0.27, 0.31 mmol) in a constant pressure titration funnel, adding redistilled tetrahydrofuran to dissolve; after pumping N2 gas three times, slowly dripping the catalyst into the three-necked flask, stirring at room temperature for 24 hours, adding 0.1 mL of pure vinyl ethyl ether to quench after the reaction is completed, stirring for another 60 minutes, and then dripping the mixture into 400 mL of rapidly stirred methanol, immediately forming a light gray precipitate, and vacuum drying the solid for 24 hours to obtain the target polymer (2.74 g, 81.32%);

[0072] 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 react to generate compound 4. Compound 4 is reacted with compound 5 to generate compound B, the obtained compound B and compound 1 are added at a molar ratio of 1:5, and an olefin metathesis reaction is carried out under the action of Ru catalyst to obtain monomer LP-B (LP-B, Mn=36kDa);

[0073] The synthesis route of 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 by monomers LP-A, LP-B, and EF, SPN-AC was constructed by monomers LP-A and C, and SPN-BD was constructed by monomers LP-B and D. The preparation method of each SPN material is to dissolve LP-A / LP-B in 3 ml of DCM, and then add a certain amount of EF / C / D as a cross-linking agent to the above solution to obtain the corresponding SPN.

[0078] The molar ratios of monomers LP-A, LP-B and cross-linker EF of SPN-EF-1-5 were 5:5 / 1, 5:5:2, 5:5:3, 5:5:4 or 5:5:5 (B21C7 fragment / P5 fragment / cross-linker), respectively.

[0079] The molar ratios of monomer LP-A and cross-linker C of SPN-AC-1-5 were 10:1, 10:2, 10:3, 10:4 or 10:5 (P5 fragment / cross-linker).

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

[0081] The corresponding SPNs were obtained above. In order to obtain samples for various tests, the samples were further hot-pressed in a mold at 80°C for 10 minutes. The self-assembly process of the monomers in the solution to form SPNs was studied. Monomers LP-A, LP-B, and EF formed a complex hydrogen spectrum ( Figure 5 ).exist Figure 5The chemical shifts of hydrogen protons F1 and F2 in monomer EF move significantly upfield, and the chemical shifts of protons L on monomer LP-B B8 The hydrogen protons E1-E4 on the monomer EF all moved toward the high field direction, which is consistent with the model experimental results, indicating that the monomers self-assembled to form SPNs. The monomers LP-A+D and LP-B+C also formed complex hydrogen spectra in the mixed solvent ( Figure 6-7 ).exist Figure 6 In the figure, the chemical shifts of the hydrogen protons C1-C4 in monomer C significantly shifted upfield, indicating that the neutral guest TPN entered the cavity of the pillar[5]arene. Figure 7 In the results, the chemical shifts of hydrogen protons D1 and D2 in monomer D significantly moved to the high field and split into two groups of signal peaks, indicating that host-guest recognition occurred between B21C7 and TAS. The results are consistent with those of LP-A+LP-B+EF, indicating that LP-A+C and LP-B+D formed two SPNs through the host-guest interaction of TPN-P5 and TAS-B21C7.

[0082] After the supramolecular polymer network was formed, when the monomer concentration of SPNs constructed by LP-A+LP-B+EF exceeded 7.5mM (LP-A=7.5mM), the polymer underwent a transformation from sol to gel. The mutual transformation of the sample from gel to sol can be achieved by heating / cooling. This is because heating reduces the binding force between the host and the guest, prompting the transformation of the sample from gel to sol; and when the temperature is lowered, the binding force between the host and the guest is restored, causing the sample to return to gel. In addition, 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 B21C7 is greater than that of TAS, which is consistent with the results of NMR. The addition of succinonitrile can also realize the transition of the sample from gel to sol. When the monomer concentration of SPNs constructed by LP-A+C exceeds 20mM (LP-A=20mM) and the monomer concentration of SPNs constructed by LP-B+D exceeds 25mM (LP-B=25mM), the polymer undergoes a transition from sol to gel. In addition, the addition of succinonitrile to LP-A+C can also realize the transition of the sample from gel to sol ( Fig. 9 a); By adding or removing K in LP-B+D + Ions can also be used to detect the interconversion of samples from gel to sol ( Fig. 9 b).

[0083] In order to verify the mechanical properties of the supramolecular polymer network structure constructed based on the host-guest interaction of TPN-P5 and TAS-B21C7, a tensile test was performed on the obtained supramolecular polymer network block sample using a universal material tensile testing machine. First, a tensile test was performed on the sample SPN-EF at room temperature at a deformation rate of 100 mm / min to explore 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 toughness calculated for SPN-EF-1-5 are shown in Figure 2. Fig.10 ab. In addition to the maximum strain, the overall mechanical properties of SPN gradually improved with the increase of crosslinker content, with Young's modulus increasing from 2.48MPa (SPN-EF-1) to 30.29MPa (SPN-EF-5), and toughness increasing from 20.92MJ m-3 (SPN-EF-1) to 41.98MJ m-3 (SPN-EF-5). The above results reveal that the crosslinking density of the supramolecular polymer network structure constructed based on the host-guest interaction of TPN-P5 and TAS-B21C7 plays an important role in determining the mechanical properties of SPN. Overall, SPN-EF-5 has balanced and comprehensive mechanical properties, and therefore it was selected as a representative sample for subsequent studies.

[0084] In order to further explore the mechanical properties of the supramolecular polymer network structure constructed by the synergistic action of the two host-guest interactions of TPN-P5 and TAS-B21 C7, and to compare and analyze the differences in mechanical properties of the supramolecular polymer structure formed when these two interactions act alone and together. Two controls were designed and synthesized. Control group one is the supramolecular polymer network SPN-AC constructed based on the TPN-P5 host-guest interaction alone; control group two is the supramolecular polymer network SPN-BD constructed based on the TAS-B21C7 host-guest interaction alone. As shown in the figure, the stress-strain curve of SPN-AC-1-5 and the calculated values ​​of Young's modulus and toughness are as follows Fig.11 ac. The results are opposite to those of the SPN-EF system. With the increase of crosslinking degree, the Young's modulus decreases from 135.48MPa (SPN-EF-1) to 11.82MPa (SPN-EF-5), the toughness decreases from 26.40MJ m-3 (SPN-EF-1) to 17.34MJ m-3 (SPN-EF-5), and the maximum strain increases with the increase of crosslinking degree. The stress-strain curve, Young's modulus and toughness calculated values ​​of SPN-BD-1-5 are shown in Fig.12As shown in b. In addition to the maximum strain, with the increase of crosslinker content, the overall mechanical properties of SPN gradually improve, Young's modulus increases from 0.89MPa (SPN-EF-1) to 19.86MPa (SPN-EF-5), and toughness increases from 9.62MJ m-3 (SPN-EF-1) to 12.70MJ m-3 (SPN-EF-5). It can be seen that SPN-AC1 has the best performance in the SPN-AC system, SPN-BD5 has the best mechanical properties in the SPN-BD system, and SPN-EF5 has the best mechanical properties in the SPN-EF system. Fig.10 cd Comparing it with SPN-EF5, it can be seen that SPN-EF5 is significantly better than the control in mechanical properties except Young's modulus, and it is determined that the supramolecular polymer constructed based on the host-guest interaction of TPN-P5 and TAS-B21 C7, in which the mechanical properties of the supramolecular polymer network constructed by the simultaneous interaction of two host-guests are better than those of the supramolecular polymer constructed by one host-guest interaction.

[0085] The thermal stability of SPN-EF5 was studied by thermogravimetric analysis (TGA). Fig.12 As shown in (a), the thermal decomposition is almost negligible before 319°C. When the temperature increases from 319°C to 528°C, the polymer thermal decomposition weight loss increases from 2.6% to 79.5%. These weight losses are attributed 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 network12(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 synthetic monomers LP-A, LP-B, EF, C, and D were used to construct three supramolecular polymer network structures, SPN-EF, SPN-AC, and SPN-BD, based on the host-guest interactions of P5-TPN and B21C7-TAS. The above-mentioned SPN series of characterization methods proved the successful construction of supramolecular polymers. The irritation effects of the formed supramolecular polymers were studied. At the same time, the gel formed when the polymer concentration exceeded a certain limit was affected by the temperature and K. + In addition, the mechanical properties of the formed supramolecular polymer network were studied, among which SPN-EF5 had the best performance.

[0087] It will be apparent to those skilled in the art that the invention is not limited to the details of the exemplary embodiments described above and that the invention can be implemented in other specific forms without departing from the spirit or essential features of the invention. Therefore, the embodiments should be considered exemplary and non-limiting in all respects, and the scope of the invention is defined by the appended claims rather than the foregoing description, and it is intended that all variations falling within the meaning and scope of the equivalent elements of the claims be included in the invention. Any reference numeral in a claim should not be considered as limiting the claim to which it relates.

[0088] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A method for preparing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether, characterized in that: The steps include: Different supramolecular polymer materials were constructed based on the host-guest interactions of P5-TPN and B21C7-TAS through monomers LP-A, LP-B, EF, C, and D. The supramolecular polymer network structures included SPN-EF-1-5, SPN-AC-1-5, and SPN-BD-1-5. The specific operations are as follows: The monomers LP-A, LP-B, and EF were used to construct SPN-EF-1-5; the monomers LP-A and C were used to construct SPN-AC-1-5; the monomers LP-B and D were used to construct SPN-BD-1-5. The preparation method of each SPN material was to dissolve LP-A / LP-B in 3 ml of DCM, and then add a certain amount of EF / C / D as a cross-linking 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:

2. The method for preparing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether according to claim 1, characterized in that: The molar ratios of the monomers LP-A, LP-B and the crosslinking agent EF in the SPN-EF-1-5 are 5:5:1, 5:5:2, 5:5:3, 5:5:4 or 5:5:5 respectively.

3. The method for preparing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether according to claim 2, characterized in that: The molar ratio of the monomer LP-A to the crosslinking agent C in the SPN-AC-1-5 is 10:1, 10:2, 10:3, 10:4 or 10:5 respectively.

4. The method for preparing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether according to claim 3, characterized in that: The molar ratio of the monomer LP-B to the cross-linking agent D in the SPN-BD-1-5 is 10:1, 10:2, 10:3, 10:4 or 10:5 respectively.

5. The method for preparing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether according to claim 1, characterized in that: The synthesis of compound LP-A comprises the following steps: taking compound A (2.00 g, 1.8 mmol) and compound 1 (2.59 g, 8.78 mmol), placing them in a three-necked flask, adding redistilled tetrahydrofuran to dissolve; placing Ru catalyst (0.30, 0.35 mmol) in a constant pressure titration funnel, adding redistilled tetrahydrofuran to dissolve; after pumping N2 gas three times, slowly dripping the catalyst into the three-necked flask, stirring at room temperature for 24 hours, adding 0.1 mL of pure vinyl ethyl ether to quench after the reaction is completed, stirring for another 60 minutes, and then dripping the mixture into 400 mL of rapidly stirred methanol, immediately forming a light gray precipitate, and vacuum drying the solid for 24 hours to obtain the target polymer (3.88 g, 83.65%); The Ru catalyst structure is as follows:

6. The method for preparing supramolecular polymer gel based on the reaction of pillar [5] aromatic hydrocarbons and crown ethers according to claim 5, characterized in that: The synthesis of monomer LP-A comprises the following steps: using cis-5-norbornene-exo-2,3-dicarboxylic anhydride as a starting material, reacting with n-butanol and 11-aminoundecanoic acid to generate compound 1 and compound 2 respectively, reacting compound 3 with compound 2 to generate compound A, feeding the obtained compound A and compound 1 at a molar ratio of 1:5, and performing olefin metathesis reaction under the action of Ru catalyst to obtain monomer LP-A (LP-A, Mn=54kDa); The synthetic route of monomer LP-A is as follows:

7. The method for preparing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether according to claim 2, characterized in that: The synthesis of compound LP-B includes the following steps: taking compound B (1.00 g, 1.6 mmol) and compound 1 (2.33 g, 7.9 mmol), placing them in a three-necked flask, adding redistilled tetrahydrofuran to dissolve; placing Ru catalyst (0.27, 0.31 mmol) in a constant pressure titration funnel, adding redistilled tetrahydrofuran to dissolve; after pumping N2 gas three times, slowly dripping the catalyst into the three-necked flask, stirring at room temperature for 24 hours, adding 0.1 mL of pure vinyl ethyl ether to quench after the reaction is completed, stirring for another 60 minutes, and then dripping the mixture into 400 mL of rapidly stirred methanol, and a light gray precipitate is immediately formed. The solid is vacuum dried for 24 hours to obtain the target polymer (2.74 g, 81.32%).

8. The method for preparing supramolecular polymer gel based on the reaction of pillar[5]arene and crown ether according to claim 7, characterized in that: The synthesis of monomer LP-B comprises the following steps: using cis-5-norbornene-exo-2,3-dicarboxylic anhydride and 5-amino-1-pentanol as starting materials to react to generate compound 4, reacting compound 4 with compound 5 to generate compound B, feeding the obtained compound B and compound 1 at a molar ratio of 1:5, and performing olefin metathesis reaction under the action of Ru catalyst to obtain monomer LP-B (LP-B, Mn=36kDa); The synthesis route of monomer LP-B is as follows: The synthetic route of compound B is as follows;

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