Ionically reversible adhesive resistant to extreme conditions, method of synthesis and two-component supramolecular adhesive

Abstract

The application discloses an ion type reversible adhesive resistant to extreme conditions, a synthesis method of the ion type reversible adhesive, and a two-component supermolecular adhesive. The ion type reversible adhesive is an imidazole type polyionic liquid connected by ether chains or alkyl chains and urethane bonds, has super-low temperature environment resistance and reversibility, can be uniformly mixed with alcohol, carboxylic acid, amide compounds and related polymers or amino acids in water or an ionic liquid, and can be prepared into a two-component supermolecular adhesive with high resistance to super-low temperature and organic solvent environments. The preparation processes of the two types of adhesives are simple, and the materials are green and environmentally friendly, so that harm of volatile organic solvents to human bodies and the environment is avoided. After cold and hot cycles, the adhesives can realize high-efficiency interfacial adhesion with materials such as stainless steel, metal, wood and glass, and the adhesion performance does not obviously decrease under super-low temperature and organic solvent conditions.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of surface interface chemistry and interface adhesion technology, and particularly relates to an ionic reversible adhesive suitable for an ultralow-temperature environment, and on the basis of which a physical modification is further realized through a supramolecular combination strategy to prepare a two-component supramolecular adhesive suitable for an ultralow-temperature and organic solvent environment. BACKGROUND

[0002] Adhesives are a class of substances that bond two or more substrates together. They are usually in liquid or semi-liquid form, which can effectively bond independent materials together when a certain external force is applied to the material interface, and facilitate the effective transfer of applied load from the interface bonding area from one substrate to another

The United States: William Andrew, 2015, 1-83

New Jersey: John Wiley & Sons, 2012

Adv. Funct. Mater., 2020, 30, 1901693; Chem. Rev., 2021, 121, 11336-11384; Adv. Mater. Technol., 2019, 4, 1900193; J. Am. Chem. Soc., 2020, 142, 5371-5379; J. Adhes. Sci. Technol., 2020, 34, 1269-1282

Adv. Mater., 2013, 25 (39): 5530-5548; Chem., 2017, 3 (5): 764-811; Chem. Soc. Rev., 2017, 46 (9): 2404-2420; Chem. Soc. Rev., 2016, 45 (2): 342-358

ACS Appl. Mater. Interfaces, 2015, 7: 13395-13404

Adv. Mater., 2010, 22 (6): 729-733; Nature Mater., 2016, 15 (4): 407-412

J. R. Soc. Interface, 2013, 10 (79): 20120759; Angew. Chem. Int. Ed., 2014, 53 (14): 3617-3621

[0003] An object of the present application is to provide a kind of ionic imidazole-based polyionic liquid reversible adhesive suitable for ultra-low temperature environment, and to provide a preparation method for the adhesive.

[0004] Another object of the present application is to use supramolecular combination strategy to modify the above-mentioned ionic imidazole-based polyionic liquid reversible adhesive physically, and to prepare a two-component supramolecular adhesive suitable for ultra-low temperature and organic solvent environment.

[0005] To achieve the above object, the ionic imidazole-based polyionic liquid reversible adhesive used in the present application is any one of the following polymers A-D:

[0006]

[0007]

[0008] In the formula, m and n respectively represent integers from 1 to 10, R1 represents

[0009] R2 represents ​Represents Cl - ,Br - PF6 - BF4 - NO3 - CF3SO3 - TFSI - Any one of them, where P represents the degree of polymerization of the ionic imidazole polyionic liquid reversible adhesive, and the molecular weight of the ionic imidazole polyionic liquid reversible adhesive is between 1,000 and 40,000.

[0010] The method for synthesizing the ionic imidazole polyionic liquid reversible adhesive is as follows: hydroxyl compound of formula I or I′ or I″ or I′″ isocyanate compound of formula II is subjected to urethane reaction to obtain polymers A to D respectively;

[0011]

[0012] In the above-mentioned method for synthesizing ionic imidazole polyionic liquid reversible adhesives, the preferred reaction temperature is 40–100°C and the reaction time is 24–48 hours.

[0013] To improve the organic solvent resistance and adhesive strength of the ionic reversible adhesive of this invention, a two-component supramolecular adhesive suitable for both ultra-low temperature and organic solvent environments is prepared by uniformly mixing it with alcohols, carboxylic acids, amides, alcohol polymers, carboxylic acid polymers, or amide polymers. Specifically, alcohols, carboxylic acids, amides, alcohol polymers, carboxylic acid polymers, amide polymers, or amino acids are dissolved in ionic liquids or water. The resulting solution is then uniformly mixed with the ionic imidazole polyionic liquid reversible adhesive of this invention at a molar ratio of 1:30 to 30:1 to obtain the target two-component supramolecular adhesive.

[0014] The carboxylic acid compound is any one of the following structural formulas:

[0015]

[0016] The alcohol compound is any one of the following structural formulas:

[0017]

[0018] The amide compound is any one of the following structural formulas:

[0019]

[0020] In the formula, R3 represents Cl, Br, F, Cl~C 11 Any straight-chain alkyl group, where x represents an integer from 1 to 10.

[0021] The alcohol polymer is any one of the following structural formulae:

[0022]

[0023] The carboxylic acid polymer is any one of the following structural formulae:

[0024]

[0025] The amide polymer has the following structural formula:

[0026] In the formula, r represents the polymerization degree, and the number average molecular weight distribution of the alcohol polymer or the carboxylic acid polymer or the amide polymer is between 1000 and 40000.

[0027] Compared with the prior art, the present application has the following beneficial effects:

[0028] (1) The ionic imidazole-based polyionic liquid reversible adhesive of the present application has simple synthesis steps, and the raw materials are cheap and easy to obtain, and the synthesis yield of the intermediate materials is high; the self-adhesive is a dominant viscoelastic fluid at room temperature or high temperature, and has good universal applicability, and shows good adhesive effect on various materials such as stainless steel, iron, copper, aluminum, glass and wood;

[0029] (2) The two-component supramolecular adhesive of the present application uses water or ionic liquid as a solvent, is green and environmentally friendly, and avoids harm to the environment and human body; the components of the two-component supramolecular adhesive can be stored for a long time, and the adhesive material can be obtained after mixing, and can be prepared at any time as needed;

[0030] (3) The ionic imidazole-based polyionic liquid reversible adhesive and the two-component supramolecular adhesive of the present application are both in liquid state, have good wettability, and have good super-low temperature resistance, and can maintain good stability at very low temperature without significant decay of the adhesive strength; moreover, the two-component supramolecular adhesive can resist organic solvents, and the samples bonded by the two-component supramolecular adhesive do not significantly decay in adhesive strength after being soaked in various organic solvents such as tetrahydrofuran, ethyl acetate, acetone, acetonitrile, petroleum ether, n-hexane, toluene, anhydrous diethyl ether and dichloromethane for a long time, and do not fall off when loaded with heavy objects and soaked for months; the interfacial bonding of the two-component supramolecular adhesive in super-low temperature environments such as liquefied natural gas (-163℃) and liquid nitrogen (-196℃) and in organic solvent systems has potential application value.

[0031] (4) The two types of adhesives obtained by the present application have viscosity decreasing with increasing temperature and increasing with decreasing temperature, and can realize high-efficiency interfacial adhesion with materials such as stainless steel, metal, wood, and glass after cold and hot cycle. The reversible interfacial adhesion can be realized by cold and hot methods, and the two-component supramolecular adhesive has no obvious decay in adhesion performance under specific organic solvents, or low temperature, or ultralow temperature conditions, that is, the adhesive strength does not obviously decay when hanging heavy objects in ultralow temperature (such as liquid nitrogen) or various organic solvents for a long time. The two-component adhesive can use water or ionic liquid as a uniform solvent, and the preparation process is simple and convenient, and the material is green and environmentally friendly, avoiding the harm of volatile organic solvents to human body and environment. On this basis, the two-component supramolecular adhesive suitable for ultralow temperature and organic solvent environment is prepared by supramolecular combination strategy. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 is a thermogravimetric diagram of adhesive a1 in example 1.

[0033] Figure 2 is a diagram of G' and G" of adhesive a1 in example 1 changing with temperature cycle.

[0034] Figure 3 is a diagram of complex viscosity of adhesive a1 in example 1 changing with temperature cycle.

[0035] Figure 4 is a gel permeation chromatogram of adhesive a1 in example 1.

[0036] Figure 5 is a thermogravimetric diagram of adhesive a2 in example 2.

[0037] Figure 6 is a diagram of G' and G" of adhesive a2 in example 2 changing with temperature cycle.

[0038] Figure 7 is a diagram of complex viscosity of adhesive a2 in example 2 changing with temperature cycle.

[0039] Figure 8 is a gel permeation chromatogram of adhesive a2 in example 2.

[0040] Figure 9 is a thermogravimetric diagram of adhesive a3 in example 3.

[0041] Figure 10 is a diagram of G' and G" of adhesive a3 in example 3 changing with temperature cycle.

[0042] Figure 11 is a diagram of complex viscosity of adhesive a3 in example 3 changing with temperature cycle.

[0043] Figure 12 is the gel permeation chromatogram of adhesive a3 in Example 3.

[0044] Figure 13 is the thermogravimetric graph of adhesive a4 in Example 4.

[0045] Figure 14 is the G' and G" with temperature cycle change graph of adhesive a4 in Example 4.

[0046] Figure 15 is the complex viscosity with temperature cycle change graph of adhesive a4 in Example 4.

[0047] Figure 16 is the gel permeation chromatogram of adhesive a4 in Example 4.

[0048] Figure 17 is the thermogravimetric graph of adhesive a1-P1 in Example 5.

[0049] Figure 18 is the G' and G" with temperature cycle change graph of adhesive a1-P1 in Example 5.

[0050] Figure 19 is the complex viscosity with temperature cycle change graph of adhesive a1-P1 in Example 5.

[0051] Figure 20 is the digital photo of adhesive a1-P1 base universal hanging weight display in Example 5.

[0052] Figure 21 is the digital photo of adhesive a1-P1 solvent resistance hanging weight display in Example 5. DETAILED DESCRIPTION

[0053] The application will be further described in conjunction with the accompanying drawings and examples, but the scope of protection of the application is not limited only to the following examples.

[0054] Example 1

[0055] 12.636 g (22 mmol) of the hydroxyl compound shown in formula I-1 and 5.502 g (22 mmol) of the isocyanate compound shown in formula II-1 were added into 150 mL of dry N,N-dimethylformamide, and the reaction was stirred at 85°C for 24 hours to obtain the ionic imidazole-based polyionic liquid reversible adhesive (denoted as a1) shown in formula A-1. Figure 1 It can be seen that the thermal analysis decomposition temperature of adhesive a1 is ≥300°C, its storage modulus (G') is less than the loss modulus (G") (see Figure 2 ), and it is macroscopically a liquid; its rheological properties have temperature dependence, the higher the temperature, the greater the fluidity, and the rheological properties are reversible between room temperature and low temperature (seeFigure 3 ). From Figure 4 it can be seen that the number average molecular weight (Mn) of a1 is 71838, the weight average molecular weight (Mw) is 146177, the Z average molecular weight (Mz) is 270645, the Z+1 average molecular weight (Mz+1) is 465303, and the polydispersity index is 2.034804. Also, the degree of polymerization (DP) estimated from the weight average molecular weight is 170.

[0056]

[0057] Example 2

[0058] 12.898 g (22 mmol) of the hydroxyl compound shown in formula I'-1 and 5.502 g (22 mmol) of the isocyanate compound shown in formula II-1 were added into 150 mL of dry N,N-dimethylformamide, and the reaction was stirred at 85°C for 24 hours to obtain the ionic imidazole-based polyionic liquid reversible adhesive shown in formula B-1 (denoted as a2). From Figure 5 it can be seen that the thermal analysis decomposition temperature of adhesive a2 is ≥ 300°C, its storage modulus (G') is less than the loss modulus (G") (see Figure 6 ), and it appears as a liquid in macroscopic view; its rheological properties have temperature dependence, and the higher the temperature, the greater the fluidity, and the rheological properties are reversible between room temperature and low temperature (see Figure 7 ). From Figure 8 it can be seen that the number average molecular weight (Mn) of a2 is 68111, the weight average molecular weight (Mw) is 163637, the Z average molecular weight (Mz) is 292779, the Z+1 average molecular weight (Mz+1) is 441876, and the polydispersity index is 2.402504. Also, the degree of polymerization (DP) estimated from the weight average molecular weight is 188.

[0059]

[0060] Example 3

[0061] 7.926 g (22 mmol) of the hydroxyl compound shown in formula I"-1 and 5.502 g (22 mmol) of the isocyanate compound shown in formula II-1 were added into 150 mL of dry N,N-dimethylformamide, and the reaction was stirred at 85°C for 24 hours to obtain the ionic imidazole-based polyionic liquid reversible adhesive shown in formula C-1 (denoted as a3). From Figure 9 it can be seen that the thermal analysis decomposition temperature of adhesive a3 is ≥ 300°C, its storage modulus (G') is less than the loss modulus (G") (see Figure 10 ), and it appears as a liquid in macroscopic view; its rheological properties have temperature dependence, and the higher the temperature, the greater the fluidity, and the rheological properties are reversible between room temperature and low temperature (see Figure 11 ). FromFigure 12 It can be seen that the number average molecular weight (Mn) of a3 is 67263, the weight average molecular weight (Mw) is 134261, the Z average molecular weight (Mz) is 213873, the Z+1 average molecular weight (Mz+1) is 299118, and the polydispersity index is 1.996070. And the degree of polymerization (DP) estimated from the weight average molecular weight is 209.

[0062]

[0063] Example 4

[0064] 8.077 g (22 mmol) of the hydroxyl compound shown in formula I”'-1 and 5.502 g (22 mmol) of the isocyanate compound shown in formula II-1 were added into 150 mL of dry N,N-dimethylformamide, and the reaction was stirred at 85°C for 24 hours to obtain the ionic imidazole-based polyionic liquid reversible adhesive shown in formula D-1 (denoted as a4). From Figure 13 It can be seen that the thermal analysis decomposition temperature of adhesive a4 is ≥300°C, its storage modulus (G') is less than the loss modulus (G") (see Figure 14 ), and it is macroscopically a liquid; its rheological properties have temperature dependence, the higher the temperature, the greater the fluidity, and the rheological properties are reversible between room temperature and low temperature (see Figure 15 )。 Figure 16 It can be seen that the number average molecular weight (Mn) of a4 is 46778, the weight average molecular weight (Mw) is 125722, the Z average molecular weight (Mz) is 216401, the Z+1 average molecular weight (Mz+1) is 319297, and the polydispersity index is 2.687651. And the degree of polymerization (DP) estimated from the weight average molecular weight is 193.

[0065]

[0066] Example 5

[0067] 0.462 g (0.154 mmol) of polyacrylic acid with a Mw of 3000 was dissolved in 2.4 mL of water, and then 0.428 g (0.500 mmol) of the ionic imidazole-based polyionic liquid reversible adhesive shown in formula A-1 was added and mixed to obtain a light yellow viscous liquid, which is a two-component supramolecular adhesive (denoted as a1-P1). From Figure 17 It can be seen that the thermal analysis decomposition temperature of adhesive a1-P1 is ≥300°C, its storage modulus (G') is less than the loss modulus (G") (see Figure 18 ), and it is macroscopically a liquid; its rheological properties have temperature dependence, the higher the temperature, the greater the fluidity, and the rheological properties are reversible between room temperature and low temperature (see Figure 19 ).

[0068] Example 6

[0069] Dissolve 0.462 g (0.154 mmol) of polyacrylic acid with a Mw of 3000 in 2.4 mL of water, then add 0.434 g (0.500 mmol) of ionic imidazole polyionic liquid reversible adhesive as shown in Formula B-1 and mix thoroughly. The resulting pale yellow viscous liquid is the two-component supramolecular adhesive (denoted as a2-P1).

[0070] Example 7

[0071] Dissolve 0.462 g (0.154 mmol) of polyacrylic acid with a Mw of 3000 in 2.4 mL of water, then add 0.321 g (0.500 mmol) of ionic imidazole polyionic liquid reversible adhesive as shown in formula C-1 and mix thoroughly. The resulting pale yellow viscous liquid is the two-component supramolecular adhesive (denoted as a3-P1).

[0072] Example 8

[0073] Dissolve 0.462 g (0.154 mmol) of polyacrylic acid with a Mw of 3000 in 2.4 mL of water, then add 0.325 g (0.500 mmol) of ionic imidazole polyionic liquid reversible adhesive as shown in formula D-1 and mix thoroughly. The resulting pale yellow viscous liquid is the two-component supramolecular adhesive (denoted as a4-P1).

[0074] Example 9

[0075] Dissolve 1.655 g (9.240 mmol) of 3-acetaminobenzoic acid in 4.0 mL of water, then add 0.428 g (0.500 mmol) of the ionic imidazole polyionic liquid reversible adhesive shown in Formula A-1 and mix thoroughly. The resulting pale yellow viscous liquid is the two-component supramolecular adhesive (denoted as a1-M1).

[0076] Example 10

[0077] Dissolve 0.546 g (9.240 mmol) of acetamide in 4.0 mL of water, then add 0.428 g (0.500 mmol) of the ionic imidazole polyionic liquid reversible adhesive shown in Formula A-1 and mix thoroughly. The resulting pale yellow viscous liquid is the two-component supramolecular adhesive (denoted as a1-M2).

[0078] Example 11

[0079] 12.636 g (22 mmol) of the hydroxyl compound shown in Formula I-1 and 5.771 g (22 mmol) of the isocyanate compound shown in Formula II-2 were added to 150 mL of dry N,N-dimethylformamide and stirred at 85 °C for 24 hours to obtain the ionic imidazole polyionic liquid reversible adhesive (denoted as b1) shown in Formula A-2. b1 has a number-average molecular weight (Mn) of 4553, a weight-average molecular weight (Mw) of 14626, a Z-average molecular weight (Mz) of 31138, a Z+1 average molecular weight (Mz+1) of 44925, and a polydispersity index of 3.2124.

[0080]

[0081] Example 12

[0082] 12.898 g (22 mmol) of the hydroxyl compound shown in Formula I'-1 and 5.771 g (22 mmol) of the isocyanate compound shown in Formula II-2 were added to 150 mL of dry N,N-dimethylformamide and stirred at 85 °C for 24 hours to obtain the ionic imidazole polyionic liquid reversible adhesive shown in Formula B-2 (denoted as b2). b2 has a number-average molecular weight (Mn) of 3102, a weight-average molecular weight (Mw) of 8333, a Z-average molecular weight (Mz) of 15403, a Z+1 average molecular weight (Mz+1) of 20961, and a polydispersity index of 2.6863.

[0083]

[0084] Example 13

[0085] 7.926 g (22 mmol) of the hydroxyl compound shown in Formula I”-1 and 5.771 g (22 mmol) of the isocyanate compound shown in Formula II-2 were added to 150 mL of dry N,N-dimethylformamide and stirred at 85 °C for 24 hours to obtain the ionic imidazole polyionic liquid reversible adhesive (denoted as b3) shown in Formula C-2. b3 has a number-average molecular weight (Mn) of 4335, a weight-average molecular weight (Mw) of 14875, a Z-average molecular weight (Mz) of 32260, a Z+1 average molecular weight (Mz+1) of 47088, and a polydispersity index of 3.4314.

[0086]

[0087] Example 14

[0088] An ionic imidazolium-based polyionic liquid reversible adhesive (denoted as b4) of formula D-2 was obtained by stirring 8.077 g (22 mmol) of the hydroxyl compound of formula I”'-1 and 5.771 g (22 mmol) of the isocyanate compound of formula II-2 in 150 mL of dry N,N-dimethylformamide at 85 °C for 24 hours. The number average molecular weight (Mn) of b4 was 5444, the weight average molecular weight (Mw) was 21511, the Z average molecular weight (Mz) was 51258, the Z+1 average molecular weight (Mz+1) was 79791, and the polydispersity index was 3.9513.

[0089]

[0090] Example 15

[0091] An ionic imidazolium-based polyionic liquid reversible adhesive (denoted as c1) of formula D-2 was obtained by stirring 12.636 g (22 mmol) of the hydroxyl compound of formula I-1 and 5.193 g (22 mmol) of the isocyanate compound of formula II-3 in 150 mL of dry N,N-dimethylformamide at 85 °C for 24 hours. The number average molecular weight (Mn) of c1 was 9684, the weight average molecular weight (Mw) was 39311, the Z average molecular weight (Mz) was 91212, the Z+1 average molecular weight (Mz+1) was 175017, and the polydispersity index was 4.0594.

[0092]

[0093] Example 16

[0094] An ionic imidazolium-based polyionic liquid reversible adhesive (denoted as c2) of formula B-3 was obtained by stirring 12.898 g (22 mmol) of the hydroxyl compound of formula I'-1 and 5.193 g (22 mmol) of the isocyanate compound of formula II-3 in 150 mL of dry N,N-dimethylformamide at 85 °C for 24 hours. The number average molecular weight (Mn) of c2 was 2226, the weight average molecular weight (Mw) was 7010, the Z average molecular weight (Mz) was 16583, the Z+1 average molecular weight (Mz+1) was 24410, and the polydispersity index was 3.1491.

[0095]

[0096] Example 17

[0097] Into 150 mL of dry N,N-dimethylformamide, 7.926 g (22 mmol) of the hydroxyl compound of Formula I"-1 and 5.193 g (22 mmol) of the isocyanate compound of Formula II-3 were added, and the reaction was stirred at 85°C for 24 hours to obtain the ionic imidazolium-based polyionic liquid reversible adhesive of Formula C-3 (denoted as c3). The number average molecular weight (Mn) of c3 was 83679, the weight average molecular weight (Mw) was 179552, the Z average molecular weight (Mz) was 368454, the Z+1 average molecular weight (Mz+1) was 639836, and the polydispersity index was 2.1457.

[0098]

[0099] Example 18

[0100] Into 150 mL of dry N,N-dimethylformamide, 8.077 g (22 mmol) of the hydroxyl compound of Formula I" -1 and 5.193 g (22 mmol) of the isocyanate compound of Formula II-3 were added, and the reaction was stirred at 85°C for 24 hours to obtain the ionic imidazolium-based polyionic liquid reversible adhesive of Formula D-3 (denoted as c4). The number average molecular weight (Mn) of c4 was 84, the weight average molecular weight (Mw) was 837, the Z average molecular weight (Mz) was 3440, the Z+1 average molecular weight (Mz+1) was 6044, and the polydispersity index was 9.9643.

[0101]

[0102] Example 19

[0103] Into 2.4 mL of water, 0.462 g (0.154 mmol) of polyacrylic acid having a Mw of 3000 was dissolved, and then 0.421 g (0.500 mmol) of the ionic imidazolium-based polyionic liquid reversible adhesive of Formula A-2 was added and mixed well to obtain a light yellow viscous liquid, which was a two-component supramolecular adhesive (denoted as b1-P1).

[0104] Example 20

[0105] Into 2.4 mL of water, 0.545 g (4.620 mmol) of succinic acid was dissolved, and then 0.421 g (0.500 mmol) of the ionic imidazolium-based polyionic liquid reversible adhesive of Formula A-2 was added and mixed well to obtain a light yellow viscous liquid, which was a two-component supramolecular adhesive (denoted as b1-M1).

[0106] Example 21

[0107] 0.462 g (0.154 mmol) of polyacrylic acid with Mw of 3000 was dissolved in 2.4 mL of water, and then 0.434 g (0.500 mmol) of the ionic imidazole-based polyionic liquid reversible adhesive shown in formula A-3 was added and mixed thoroughly to obtain a light yellow viscous liquid, which was the two-component supramolecular adhesive (denoted as c1-P1).

[0108] Example 22

[0109] 0.545 g (4.620 mmol) of succinic acid was dissolved in 2.4 mL of water, and then 0.434 g (0.500 mmol) of the ionic imidazole-based polyionic liquid reversible adhesive shown in formula A-3 was added and mixed thoroughly to obtain a light yellow viscous liquid, which was the two-component supramolecular adhesive (denoted as c1-M1).

[0110] To accurately test the adhesive strength of the adhesive of the present application, the sample interfacial bonding process includes the following steps: taking a stainless steel substrate as an example, the surface of the substrate should be cleaned before the sample is prepared to ensure that there is no dust, liquid or other impurities that can damage the adhesive strength. To ensure the repeatability of the adhesive strength, a 600-mesh fine sandpaper is used to polish the stainless steel substrate. The shear strength is tested by a single lap joint method, and the bonding area is strictly fixed (200 mm 2 ) on both substrates. 100 mg of the adhesive is uniformly coated on the 200 mm 2 area of the substrate, and after preheating in a temperature-controlled oven for 30 min to ensure good interfacial wettability, the two substrates are overlapped at the bonding area and pressed together under a pressure of 2 kg to ensure that the bonding area is tightly attached. The sample is then placed in a room temperature environment and cooled under a load of 2 kg to complete the interfacial bonding.

[0111] The interfacial bonding test is completed by a universal material testing machine (WDW-100M, Jinan Zhonglu Chang Testing Machine Co., Ltd.), and the test method is in accordance with the national standard GB / T 712-1986 single lap shear mode. The specific process is as follows: the prepared interfacial bonding sample is fixed on the upper and lower clamps, and a tensile shear rate of 20 mm / min is applied in the opposite direction until the lap shear sample is separated or broken. At this time, the highest point in the shear force-displacement curve is the peak force of the damaged shear sample, which is the maximum interfacial adhesion. According to the measured bonding area, the adhesive shear tensile strength can be calculated according to formula (1). Each group of shear tests is tested 7 times, and the highest and lowest points are removed.

[0112] τ = P / B·L (1)

[0113] In the formula: τ—adhesive shear tensile strength, MPa;

[0114] P—interfacial adhesion, N;

[0115] B - width of the overlap surface of the sample, mm

[0116] L - length of the overlap surface of the sample, mm.

[0117] According to the above procedure, the adhesive a1, a1-P1 was used to bond 200 mm 2 long samples of 304 stainless steel, copper, aluminum, iron, pine wood and tempered glass, respectively. The adhesive strength and the average adhesive strength of 5 tests are shown in Table 1, Table 2. a1-a4, b1-b4, c1-c4, a1-P1-a4-P1 were used to bond 200 mm 2 long samples of 304 stainless steel, respectively. The adhesive strength and the average adhesive strength of 5 tests are shown in Table 3-6.

[0118] Table 1 Adhesive strength (MPa) of adhesive a1 to various substrates

[0119]

[0120] Table 2 Adhesive strength (MPa) of adhesive a1-P1 to various substrates

[0121]

[0122]

[0123] Table 3 Adhesive strength (MPa) of adhesive a1, a2, a3 and a4 to 304 stainless steel substrate

[0124]

[0125] Table 4 Adhesive strength (MPa) of adhesive a1-P1, a2-P1, a3-P1 and a4-P1 to 304 stainless steel substrate

[0126]

[0127] Table 5 Adhesive strength (MPa) of adhesive b1, b2, b3 and b4 to 304 stainless steel substrate

[0128]

[0129]

[0130] Table 6 Adhesive strength (MPa) of adhesive c1, c2, c3 and c4 to 304 stainless steel substrate

[0131]

[0132] The experimental results show that the adhesive a1 obtained in Example 1 was used to bond 200 mm 2Samples were prepared using materials such as 304 stainless steel, copper, aluminum, iron, pine wood, and glass. The sample prepared on a stainless steel substrate could support a weight of over 100 kg. A 200 mm section was bonded using adhesive a1-P1 obtained in Example 5. 2 Samples were made from materials such as 304 stainless steel, copper, aluminum, iron, pine wood, and glass. Samples prepared on a stainless steel substrate can bear a weight of over 100 kg. See the image below. Figure 20 As shown. Further, the adhesive a1 obtained in Example 1 was used to bond a 200mm section. 2 The 304 stainless steel sample, after separation, the adhesive residue on the matrix can be bonded again after heating, and the bonding strength is not significantly reduced compared with the first bonding. This cycle can be repeated at least 20 times. The bonding strength test results for each bonding are shown in Table 7.

[0133] The adhesive a1-P1 obtained in Example 5 above is used to bond 200mm. 2 The 304 stainless steel samples were immersed in different solvents such as petroleum ether, n-hexane, toluene, anhydrous diethyl ether, dichloromethane (DCM), tetrahydrofuran (THF), ethyl acetate (EA), acetone, acetonitrile and water for 60 days. The bonding strength and average bonding strength of the five tests are shown in Table 8.

[0134] Table 7. Adhesive strength (MPa) of adhesive a1 during multiple bonding cycles.

[0135]

[0136]

[0137] Table 8. Adhesive strength (MPa) of adhesives a1-P1 after immersion in various solvents for 60 days.

[0138]

[0139] The adhesive a1-P1 obtained in Example 5 above is used to bond 200mm. 2 A 304 stainless steel sample, loaded with a 2.0 kg weight, was immersed in solvents including petroleum ether, n-hexane, toluene, anhydrous diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, acetonitrile, water, and seawater. The results showed that the sample remained intact for more than two months without detachment. A photograph of the sample is shown below. Figure 21 As shown.

[0140] The adhesive a1 obtained in Example 1 and the adhesive a1-P1 obtained in Example 5 were bonded together for 200 mm. 2 The 304 stainless steel samples were immersed in liquid nitrogen for 1 to 7 days. Their adhesive strength decreased, but they still maintained high adhesive performance. The test results are shown in Tables 9 and 10.

[0141] Table 9 Adhesive a1 bonding strength (MPa) after soaking in liquid nitrogen (-196 °C)

[0142]

[0143] Table 10 Adhesive a1-P1 bonding strength (MPa) after soaking in liquid nitrogen (-196 °C)

[0144]

[0145] From the above experimental results, it can be seen that the adhesives a1, a1-P1 exhibit good adhesion to 304 stainless steel, copper, aluminum, iron, pine, glass and other materials; the adhesion and separation can be controlled by temperature, and the residual adhesive on the joint after release can be easily removed with ethanol; the well-adhered samples can be separated on demand by heating or washing with ethanol solution; the ionic imidazolium-based polyionic liquid reversible adhesive samples after separation can be re-adhered without the need to add adhesive, and the number of cycles is large and the adhesion strength does not significantly decay; the two-component supramolecular adhesive can withstand organic solvents, and the samples adhered by it do not significantly decay in adhesion strength after soaking in various organic solvents such as petroleum ether, n-hexane, toluene, anhydrous diethyl ether, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, acetonitrile, etc. for a long time, and do not fall off while loading heavy objects for months; it has good ultra-low temperature resistance and maintains good stability in liquid gases such as liquid nitrogen, and its adhesion strength does not significantly decay in a liquid nitrogen environment.

Claims

1. An ionic imidazolium-based polyionic liquid reversible adhesive suitable for use in ultra-low temperature environments, characterized in that, The adhesive is any one of the following polymers A-D: A B C D wherein m and n each represent an integer of 1 to 10, R1represents , R2represents , , , , , , , , , , , represents any one of Cl - , Br - , PF6 - , BF4 - , NO3 - , CF3SO3 - , TFSI - , and P represents the degree of polymerization of an ionic imidazole-based polyionic liquid reversible adhesive having a number average molecular weight distribution of 1000 to 40,000.

2. The method of synthesis of the ionic imidazolium-based polyionic liquid reversible adhesive of claim 1, characterized in that, The hydroxyl compound shown in formula I or I' or I" or I'" is subjected to urethane reaction with the isocyanate compound shown in formula II, to obtain polymers A-D, respectively. 。 3. The method for synthesizing the ionic imidazole polyionic liquid reversible adhesive according to claim 2, characterized in that, The reaction temperature is 40-100 DEG C, and the reaction time is 24-48 hours.

4. A two-component supramolecular adhesive suitable for use in both ultra-low temperature and organic solvent environments, characterized in that, The alcohol compound or carboxylic acid compound or amide compound or alcohol polymer or carboxylic acid polymer or amide polymer or amino acid is dissolved in ionic liquid or water, and the obtained solution is uniformly mixed with the ionic imidazole-based polyionic liquid reversible adhesive according to claim 1 at a mass ratio of 1:30-30:1, to obtain the target two-component supramolecular adhesive.

5. The two-component supramolecular adhesive according to claim 4, which is suitable for use in both ultra-low temperature and organic solvent environments, characterized in that, The carboxylic acid compound is any one of the following structural formulas: The alcohol compound is any one of the following structural formulas: The amide compound is any one of the following structural formulas: In the formula, R3 represents Cl, Br, F, Cl~C 11 Any straight-chain alkyl group, where x represents an integer from 1 to 10.

6. The two-component supramolecular adhesive according to claim 4, which is suitable for use in both ultra-low temperature and organic solvent environments, characterized in that, The alcohol polymer is any one of the following structural formulas: The carboxylic acid polymer has a structural formula of: The structural formula of the amide polymer is: In the formula, r represents the polymerization degree, and the number average molecular weight distribution of the alcohol polymer or carboxylic acid polymer or amide polymer is between 1000 and 40000.

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