Adhesive composition, adhesive and applications, composite parts

Abstract

The present application relates to the technical field of adhesives, and particularly relates to an adhesive composition, an adhesive, application of the adhesive, and a composite part.The adhesive composition comprises: an epoxy-based ionic liquid resin having a structure shown in formula I and / or formula II, a vinyl ionic liquid resin having a structure shown in formula III, and a complex curing agent; wherein m and n are each independently selected from integers from 1 to 10; a and b are each independently selected from 1 to 10; x is selected from integers from 1 to 10, y is selected from integers from 0 to 10, L ‑ is selected from anions.The adhesive provided by the present application is prepared by reaction of ionic liquid resins with specific structures, has good bonding force, low viscosity, can make up for the gap between the metal sealing head and the plastic liner, and has good low-temperature toughness, thereby improving the sealing performance of the plastic liner.

Description

Technical Field

[0001] This invention relates to the field of adhesive technology, specifically to an adhesive composition, an adhesive, an application of an adhesive, and a composite component. Background Technology

[0002] Hydrogen fuel cell vehicles are developing steadily. Currently, there are four types of hydrogen storage cylinders: all-metal cylinders, metal-lined fiber-wound cylinders, metal-lined fully-wound fiber cylinders, and non-metallic-lined fully-wound fiber cylinders. The advantage of non-metallic-lined fiber-wound cylinders compared to the other three types is their lighter weight, which better meets the requirements for hydrogen storage density per unit mass, while avoiding severe hydrogen embrittlement. The mainstream manufacturing processes for type IV liners generally include rotational molding, blow molding, and injection molding. Injection molding is more widely used due to its dimensional stability, low cost, flexible sealing structure design, and ability to produce thin-walled products.

[0003] Plastic liner fabricated by injection molding typically consists of a metal end cap and an injection-molded part, which are then assembled and welded together. However, due to differences in the machining precision of the metal part and the precision of the plastic during processing, as well as the varying shrinkage rates of the metal and plastic during inflation and deflation, gaps of varying sizes often exist between the metal end cap and the injection-molded part during use. Some of these gaps can be filled by resin during subsequent winding, but a significant portion remains. Because ordinary winding resin is an epoxy system, it has poor toughness and low adhesion to both plastic and metal. During subsequent cycles, repeated thermal expansion and contraction, as well as deformation and compression of the liner, can easily cause it to detach from one of the phases.

[0004] To provide an effective way to improve the sealing performance between the metal end cap and the plastic inner liner, reduce hydrogen leakage, and have good fatigue tear resistance in view of the hydrogen filling and releasing characteristics, it is urgent to develop an adhesive that is easy to use, has good adhesion to both metals and plastics, and has good toughness. Summary of the Invention

[0005] The purpose of this invention is to overcome the above-mentioned technical problems and provide an adhesive composition, an adhesive, an application of the adhesive, and a composite component; the adhesive is prepared by reaction of an ionic liquid resin with a specific structure, has good bonding strength, low viscosity, can fill the gap between the metal end cap and the plastic liner, and has good low-temperature toughness, thereby improving the sealing performance of the plastic liner.

[0006] To achieve the above objectives, a first aspect of the present invention provides an adhesive composition comprising: an epoxy-based ionic liquid resin having the structure shown in Formula I and / or Formula II, a vinyl-based ionic liquid resin having the structure shown in Formula III, and a compounded curing agent;

[0007]

[0008] Where m and n are each independently selected from integers 1-10; a and b are each independently selected from integers 1-10; x is selected from integers 1-10; y is selected from integers 0-10; L - Selected from anions.

[0009] Preferably, the compound curing agent comprises: a first curing agent and a second curing agent, wherein the first curing agent is selected from amine curing agents and / or acid anhydride curing agents; and the second curing agent is selected from free radical initiators.

[0010] The third aspect of the present invention provides the application of the adhesive provided in the second aspect in a plastic liner, preferably in a carbon fiber wound hydrogen storage cylinder with a plastic liner.

[0011] A fourth aspect of the present invention provides a composite component comprising an upper metal end cap and a lower gas cylinder liner, and an adhesive layer disposed between the metal end cap and the gas cylinder liner.

[0012] The adhesive layer is obtained by curing the adhesive provided by the second aspect.

[0013] Compared with the prior art, the present invention has the following advantages:

[0014] (1) The present invention uses epoxy ionic liquid resin with the structure shown in Formula I and / or Formula II, and vinyl ionic liquid resin with the structure shown in Formula III as effective components of adhesive. Since the specific ionic liquid resin has imidazole ring, epoxy group, carbon-carbon double bond, amide, and anion, the specific ionic liquid resin reacts with a specific compound curing agent to obtain an adhesive with a cross-linked network structure. In this network structure, the imidazole ring, hydroxyl group and amide can generate a large number of hydrogen bonds with each other. In particular, the specific anion can also participate in the formation of hydrogen bond network structure, thereby increasing the toughness and low temperature resistance of the adhesive.

[0015] Meanwhile, due to the characteristics of ionic liquid resins, charge interactions can also greatly increase toughness at low temperatures;

[0016] (2) The adhesive provided by the present invention effectively improves the toughness and low temperature resistance of the adhesive by optimizing the amount of epoxy ionic liquid resin and vinyl ionic liquid resin, especially by further optimizing the amount of Formula I and Formula II in the epoxy ionic liquid resin.

[0017] (3) The adhesive provided by the present invention is applied to plastic liner, especially to carbon fiber wound hydrogen storage cylinders with plastic liner. The adhesive can quickly fill the gap between the metal end cap and the plastic liner, and improve the sealing performance of the liner for hydrogen. At the same time, the adhesive provided by the present invention has good toughness after curing, and will not break due to pressure deformation or gap changes of the liner during subsequent use. Attached Figure Description

[0018] Figure 1 This is a schematic diagram of the structure of a composite component provided by the present invention;

[0019] Figure 2 This is a schematic diagram of the coating process of the adhesive provided by the present invention;

[0020] Figure 3 This is a schematic diagram of the formation of the adhesive layer provided by the present invention.

[0021] Explanation of reference numerals in the attached figures

[0022] 1. Metal end cap; 2. Base; 3. Gas cylinder liner; 4. Contact surface; 5. Scraper; 6. Flow transfer pump; 7. Adhesive; 8. Adhesive layer. Detailed Implementation

[0023] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] In this invention, unless otherwise specified, "first" and "second" do not indicate a sequence or limit the various materials or steps, but are used only to distinguish or indicate that they are not the same material or step. For example, "first" and "second" in "first curing agent" and "second curing agent" are only used to indicate that they are not the same curing agent.

[0025] A first aspect of the present invention provides an adhesive composition comprising: an epoxy-based ionic liquid resin having the structure shown in Formula I and / or Formula II, a vinyl-based ionic liquid resin having the structure shown in Formula III, and a compounded curing agent;

[0026]

[0027] Where m and n are each independently selected from integers 1-10; a and b are each independently selected from integers 1-10; x is selected from integers 1-10; y is selected from integers 0-10; L - Selected from anions.

[0028] In this invention, unless otherwise specified, the adhesive composition comprises: an epoxy-based ionic liquid resin having the structure shown in Formula I and a vinyl-based ionic liquid resin having the structure shown in Formula III; or, the adhesive composition comprises: an epoxy-based ionic liquid resin having the structure shown in Formula II and a vinyl-based ionic liquid resin having the structure shown in Formula III; or, the adhesive composition comprises: an epoxy-based ionic liquid resin having the structures shown in Formula I and Formula II, and a vinyl-based ionic liquid resin having the structure shown in Formula III.

[0029] In some embodiments of the present invention, preferably, the mass ratio of the epoxy-based ionic liquid resin to the vinyl-based ionic liquid resin is 0.1-10:1, for example, 0.1:1, 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 8:1, 10:1, and any value within any range of two such values, preferably 0.1-4:1. In the present invention, by adjusting the above mass ratio, it is beneficial to optimize the overall performance of the adhesive; a mass ratio less than 0.1:1 or greater than 10:1 will reduce the toughness and strength of the adhesive.

[0030] In some embodiments of the present invention, more preferably, when the epoxy-based ionic liquid resin has the structures shown in Formula I and Formula II, the ratio of the compound shown in Formula I to the compound shown in Formula II is 0.1-5:1, for example, 0.1:1, 0.2:1, 0.5:1, 0.8:1, 1:1, 1.5:1, 2:1, 3:1, 5:1, and any value within the range of any two values, preferably 0.5-2:1. In the present invention, further controlling the amount of the structures shown in Formula I and Formula II in the epoxy-based ionic liquid resin is beneficial to improving the low-temperature performance of the adhesive, especially the low-temperature elongation and low-temperature bond strength.

[0031] In some specific embodiments of the present invention, the mass ratio of the epoxy ionic liquid resin to the vinyl ionic liquid resin is 0.1-10:1, preferably 0.1-4:1; wherein, when the epoxy ionic liquid resin has the structures shown in Formula I and Formula II, the mass ratio of the compound shown in Formula I to the compound shown in Formula II is 0.1-5:1, preferably 0.5-2:1.

[0032] In some embodiments of the present invention, preferably, L - Selected from NTf2 - Cl - I - ,Br - F - OH - Ac - CN- HS - ,

[0033] Preferred from NTf2 - Cl - OH - Ac - CN - HS - More preferably selected from NTf2 - Cl - .

[0034] In some embodiments of the present invention, in Formula I, m and n are each independently selected from integers from 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, preferably integers from 1 to 5, and more preferably integers from 1 to 3.

[0035] In some embodiments of the present invention, in Formula II, a and b are each independently selected from integers from 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, preferably integers from 1 to 5, and more preferably integers from 1 to 3.

[0036] In some embodiments of the present invention, in Formula III, x is selected from integers from 1 to 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, preferably integers from 1 to 5, more preferably integers from 1 to 3; y is selected from integers from 0 to 10, for example, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, preferably integers from 0 to 5, more preferably integers from 0 to 3.

[0037] In this invention, the source of the epoxy-based ionic liquid resin having the structure shown in Formula I has a wide range of choices; it can be obtained commercially or prepared.

[0038] In some embodiments of the present invention, the epoxy-based ionic liquid resin having the structure shown in Formula I is prepared by the following method:

[0039] (1) Imidazole and the compound shown in Formula I-1 were subjected to a first substitution reaction in a first solvent to obtain the compound shown in Formula I-2;

[0040] (2) The compound shown in Formula I-2 and the compound shown in Formula I-3 were subjected to a second substitution reaction in a second solvent to obtain the compound shown in Formula I-4;

[0041] (3) Optionally, the compound shown in Formula I-4 and the ion exchanger of general formula ML are subjected to an ion exchange reaction in a third solvent to obtain the compound shown in Formula I-5;

[0042] (4) The compound shown in Formula I-4, or the compound shown in Formula I-5, is oxidized with an oxidant in a fourth solvent to obtain a structure having the structure shown in Formula I.

[0043]

[0044]

[0045] Wherein, X is selected from Cl, I, Br, F; m and n are each independently selected from integers from 1 to 10, preferably integers from 1 to 5, and more preferably integers from 1 to 3; L - The ion exchanger is selected from anions; M in the ion exchanger is selected from alkali metal ions.

[0046] In some embodiments of the present invention, in step (1), the conditions for the first substitution reaction include: a temperature of 10-150°C and a time of 0.1-48 h; the molar ratio of the imidazole and the compound represented by formula I-1 is 1:1-1.1, preferably 1:1-1.05; the first solvent is selected from aprotic solvents, preferably selected from THF and / or dioxane.

[0047] In some embodiments of the present invention, in step (2), the conditions for the second substitution reaction include: a temperature of 10-150°C and a time of 0.1-96 h; the molar ratio of the compound shown in Formula I-2 to the compound shown in Formula I-3 is 1:1-1.1, preferably 1:1-1.05; the second solvent is selected from aprotic solvents, preferably from THF and / or dioxane.

[0048] In some embodiments of the present invention, in step (3), the conditions for the ion exchange reaction include: a temperature of 10-150°C and a time of 0.1-96 h; the molar ratio of the compound represented by formula I-4 to the ion exchanger is 1:1-1.1, preferably 1:1-1.05; and the third solvent is selected from at least one of THF, dioxane, methanol, dichloromethane, and acetonitrile.

[0049] In some embodiments of the present invention, in step (4), the conditions of the oxidation reaction include: a temperature of 10-150°C and a time of 0.1-96 h; the oxidant is selected from peroxy acids, including but not limited to mCPBA; and the fourth solvent is independently selected from at least one of THF, dioxane, methanol, dichloromethane and acetonitrile.

[0050] In this invention, the source of the epoxy ionic liquid resin having the structure shown in Formula II has a wide range of choices; it can be obtained commercially or prepared.

[0051] In some embodiments of the present invention, preferably, the epoxy-based ionic liquid resin having the structure shown in Formula II is prepared by the following method:

[0052] (1') In the presence of a first base and a first solvent, the compound shown in formula II-1 is subjected to a first substitution reaction to obtain the compound shown in formula II-2;

[0053] (2') In the presence of a second base and a second solvent, the compound shown in formula II-2 and imidazole are subjected to a second substitution reaction to obtain the compound shown in formula II-3;

[0054] (3') In the presence of a third solvent, the compound shown in formula II-3 and the compound shown in formula II-4 are subjected to a third substitution reaction to obtain the compound shown in formula II-5;

[0055] (4') Optionally, in the presence of a fourth solvent, the compound shown in Formula II-5 and an ion exchanger of general formula ML are subjected to an ion exchange reaction to obtain the compound shown in Formula II-6;

[0056] (5') In the presence of a fifth solvent, the compound shown in Formula II-5, or the compound shown in Formula II-6, is oxidized with an oxidant to obtain a structure having the structure shown in Formula II;

[0057]

[0058]

[0059] Wherein, Q is selected from OTs, F, Cl, Br, I; X is selected from F, Cl, Br, I; a and b are each independently selected from integers from 1 to 10, preferably from integers from 1 to 5, and more preferably from integers from 1 to 3; in the ion exchanger, M is selected from alkali metal ions, L - Selected from anions.

[0060] In some embodiments of the present invention, preferably, in step (1'), the conditions for the first substitution reaction include: a temperature of 15-40°C, preferably 20-30°C; a time of 0.1-48 h, preferably 0.1-36 h; the first base is selected from at least one of NaOH, KOH, RbOH, CsOH, NaH and sodium alkoxide; the first solvent is selected from aprotic solvents, preferably at least one of THF, dioxane and DMF.

[0061] In some embodiments of the present invention, preferably, in step (2'), the molar ratio of the compound represented by formula II-1 to imidazole is 1:2-2.1, more preferably 1:2-2.05; the conditions for the second substitution reaction include: a temperature of 10-150°C, more preferably 50-100°C; a time of 0.1-96 h, more preferably 0.1-36 h; the second base is selected from at least one of NaOH, KOH, RbOH, CsOH, NaH and sodium alkoxide; the second solvent is selected from aprotic solvents, preferably at least one of THF, dioxane and DMF.

[0062] In some embodiments of the present invention, preferably, in step (3'), the molar ratio of the compound represented by formula II-3 and the compound represented by formula II-4 is 1:2-2.1, more preferably 1:2-2.05; the conditions for the third substitution reaction include: a temperature of 10-150°C, more preferably 50-100°C; a time of 0.1-96 h, more preferably 0.1-72 h; and the third solvent is selected from aprotic solvents, preferably at least one of THF, dioxane, and DMF.

[0063] In some embodiments of the present invention, preferably, in step (4'), the molar ratio of the compound represented by formula II-5 to the ion exchanger is 1:2-2.1, more preferably 1:2-2.05; the conditions for the ion exchange reaction include: a temperature of 10-150°C, more preferably 20-90°C; a time of 0.1-96 h, more preferably 0.1-72 h; and the fourth solvent is selected from at least one of THF, dioxane, methanol, dichloromethane, and acetonitrile.

[0064] In some embodiments of the present invention, preferably, in step (5'), the conditions of the oxidation reaction include: a temperature of 10-150°C; a time of 0.1-96 h; the oxidant is selected from peroxy acids, including but not limited to mCPBA; and the fifth solvent is independently selected from at least one of THF, dioxane, methanol, dichloromethane, and acetonitrile.

[0065] In this invention, the source of the vinyl ionic liquid resin having the structure shown in Formula III has a wide range of choices; it can be obtained commercially or prepared.

[0066] In some embodiments of the present invention, the vinyl ionic liquid resin having the structure shown in Formula III is prepared by the following method:

[0067] (1”) In the first solvent, the compound shown in Formula III-1 and the compound shown in Formula III-2 are subjected to a substitution reaction to obtain the compound shown in Formula III-3;

[0068] (2”) In an optional second solvent, the compound shown in Formula III-3 and an ion exchanger of general formula ML are subjected to an ion exchange reaction to obtain a structure having the structure shown in Formula III;

[0069]

[0070] Wherein, x is selected from integers 1-10, preferably integers 1-5, more preferably integers 1-3; y is selected from integers 0-10, preferably integers 0-5, more preferably integers 0-3; L - The components are selected from anions, X is selected from Cl, I, Br, F; M is selected from alkali metals, specifically Li, Na, K.

[0071] In some embodiments of the present invention, in step (1”), the conditions for the substitution reaction include: a temperature of 10-150°C and a time of 0.1-96 h; the molar ratio of the compound represented by Formula III-1 to the compound represented by Formula III-2 is 1:1-1.1, preferably 1:1-1.05; the first solvent is selected from organic solvents, preferably selected from THF, dioxane, acetonitrile, etc.

[0072] In some embodiments of the present invention, in step (2”), the conditions for the ion exchange reaction include: a temperature of 10-150°C and a time of 0.1-96 h; the molar ratio of the compound represented by formula III-3 to the ion exchanger is 1:1-1.1, preferably 1:1-1.05; the second solvent is selected from organic solvents, preferably selected from THF, dioxane, methanol, dichloromethane, etc.

[0073] In some embodiments of the present invention, preferably, the compound curing agent includes: a first curing agent and a second curing agent, wherein the first curing agent is selected from amine curing agents or acid anhydride curing agents; and the second curing agent is selected from free radical initiators.

[0074] In some embodiments of the present invention, preferably, the mass ratio of the epoxy ionic liquid resin to the first curing agent is 1:0.1-4, for example, 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:1.5, 1:2, 1:4, and any value within the range of any two values, preferably 1:0.1-2, more preferably 1:0.2-1.

[0075] In some embodiments of the present invention, preferably, the mass ratio of the vinyl ionic liquid resin and the second curing agent is 1:0.001-0.04, for example, 1:0.001, 1:0.002, 1:0.005, 1:0.008, 1:0.01, 1:0.012, 1:0.015, 1:0.018, 1:0.02, 1:0.04, and any value within any range of any two values, preferably 1:0.001-0.02, more preferably 1:0.001-0.01.

[0076] In some embodiments of the present invention, preferably, the amine curing agent is selected from diamine curing agents, and more preferably from at least one of isophorone diamine, 4,4'-diaminodiphenyl ether, hydroxyethyl ethylenediamine, diethylenetriamine, aminoethylpiperazine, 1,2-diaminocyclohexane and methylene dicyclohexaneamine.

[0077] In some embodiments of the present invention, preferably, the anhydride curing agent is selected from diacid anhydride curing agents, and more preferably from at least one of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride and methylnadic anhydride.

[0078] In some embodiments of the present invention, preferably, the free radical initiator is selected from at least one of sodium persulfate, potassium persulfate, azobisisobutyronitrile (AIBN), azobisisoheptanenitrile, dimethyl azobisisobutyrate, peroxybenzoic acid, peroxymethyl ethyl ketone, benzoyl peroxide, and cyclohexanone peroxide.

[0079] In this invention, the adhesive composition may include, in addition to: an epoxy ionic liquid resin having the structure of Formula I and / or Formula II, a vinyl ionic liquid resin having the structure of Formula III, a first curing agent, and a second curing agent, conventional epoxy resin and / or vinyl resin.

[0080] In some embodiments of the present invention, preferably, the adhesive composition further includes: epoxy resin and / or vinyl resin.

[0081] In some embodiments of the present invention, more preferably, when the adhesive composition further includes epoxy resin, the mass ratio of the epoxy-based ionic liquid resin to the epoxy resin is 1:0.1-5, for example, 1:0.1, 1:0.2, 1:0.5, 1:0.8, 1:1, 1:1.5, 1:2, 1:3, 1:5, and any value within the range of any two values, preferably 1:0.1-2.

[0082] In some embodiments of the present invention, more preferably, when the adhesive composition further includes a vinyl resin, the mass ratio of the epoxy ionic liquid resin to the vinyl resin is 1:0.1-2, for example, 1:0.1, 1:0.2, 1:0.5, 1:0.6, 1:0.8, 1:1, 1:2, and any value within the range of any two values, preferably 1:0.5-1.

[0083] In some embodiments of the present invention, more preferably, when the adhesive composition further includes epoxy resin and vinyl resin, the mass ratio of the epoxy ionic liquid resin, epoxy resin and vinyl resin is 1:0.1-5:0.1-2, preferably 1:0.1-2:0.5-1.

[0084] In this invention, preferably, the epoxy resin is selected from at least one of the following: diglycidyl phthalate, E51 type epoxy resin, E44 type epoxy resin, triglycidyl m-aminophenol, tetraglycidyl diaminodiphenylmethane, diglycidyl p-aminophenol, 3-ESL aminomethylcyclohexane, diglycidyl hexahydrophthalic acid, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl tetrahydrophthalic acid, diglycidyl methyltetrahydrophthalic acid, and diglycidyl methylenetetrahydrophthalic acid.

[0085] In this invention, preferably, the vinyl resin is selected from at least one of 1-vinyl-3-methylimidazolium chloride, bisphenol A epoxy vinyl ester, methyl methacrylate, glycidyl methacrylate, and glycidyl acrylate.

[0086] In some embodiments of the present invention, the adhesive composition comprises an epoxy-based ionic liquid resin having the structure shown in Formula I and / or Formula II, a vinyl-based ionic liquid resin having the structure shown in Formula III, and a compounded curing agent; or...

[0087] The adhesive composition comprises an epoxy ionic liquid resin having the structure of Formula I and / or Formula II, a vinyl ionic liquid resin having the structure of Formula III, a compound curing agent, an epoxy resin, and / or a vinyl resin.

[0088] A second aspect of the present invention provides an adhesive, said adhesive being prepared by reacting the adhesive composition provided in the first aspect;

[0089] The reaction conditions are as follows: temperature 10-130℃; rotation speed 100-1000rpm; time 0.1-5h.

[0090] In this invention, more preferably, the reaction conditions are as follows: temperature is 10-130℃, for example, 10℃, 20℃, 40℃, 60℃, 70℃, 80℃, 90℃, 100℃, 130℃, and any value within the range of any two values, preferably 60-90℃; rotation speed is 100-1000rpm, for example, 100rpm, 300rpm, 400rpm, 500rpm, 600rpm, 800rpm, 1000rpm, and any value within the range of any two values, preferably 300-800rpm; time is 0.1-5h, preferably 0.1-2h.

[0091] In some embodiments of the present invention, more preferably, the reaction process includes: subjecting the epoxy-based ionic liquid resin and the first curing agent to a first reaction; subjecting the vinyl epoxy resin and the second curing agent to a second reaction; and subjecting the product of the second reaction to a third reaction with the epoxy-based ionic liquid resin.

[0092] In this invention, unless otherwise specified, the conditions for the first reaction, the second reaction, and the third reaction are all the same as the conditions for the aforementioned reaction, and they are carried out simultaneously.

[0093] The first adhesive provided by the present invention is prepared by reacting a first adhesive composition, namely, by reacting an adhesive composition consisting of an epoxy ionic liquid resin having the structure of Formula I and / or Formula II, a vinyl ionic liquid resin having the structure of Formula III, a first curing agent, and a second curing agent.

[0094] The second adhesive provided by the present invention is prepared by reacting a second adhesive composition, namely, by reacting an adhesive composition consisting of an epoxy ionic liquid resin having the structure of Formula I and / or Formula II, a vinyl ionic liquid resin having the structure of Formula III, a first curing agent, a second curing agent, an epoxy resin and / or a vinyl resin.

[0095] A third aspect of the present invention provides the application of the adhesive provided in the second aspect in a plastic liner, preferably in a carbon fiber wound hydrogen storage cylinder with a plastic liner.

[0096] A fourth aspect of the present invention provides a composite component comprising an upper metal end cap and a lower gas cylinder liner, and an adhesive layer disposed between the metal end cap and the gas cylinder liner.

[0097] The adhesive layer is obtained by curing the adhesive provided by the second aspect.

[0098] In some embodiments of the present invention, preferably, the curing conditions include: a temperature of 10-130°C, preferably 60-90°C; and a time of 0.1-5h, preferably 0.1-2h.

[0099] The structural schematic diagram of the composite component provided by this invention is shown below. Figure 1 As shown, by Figure 1 It can be seen that the composite component consists of a metal end cap 1 on top, a gas cylinder liner 3 on the bottom, and an adhesive layer 8 between the two.

[0100] In some embodiments of the present invention, preferably, the thickness of the adhesive layer is 0.001-0.32 mm, for example, 0.001 mm, 0.005 mm, 0.01 mm, 0.05 mm, 0.1 mm, 0.15 mm, 0.2 mm, 0.25 mm, 0.3 mm, 0.32 mm, and any value within the range of any two values, preferably 0.01-0.3 mm.

[0101] The adhesive layer prepared by the adhesive provided by the present invention has good elongation at break, bonding strength and low temperature resistance.

[0102] In some embodiments of the present invention, preferably, the adhesive layer has a bonding strength at 25°C ≥ 18 MPa, for example, 18 MPa, 20 MPa, 21 MPa, 22 MPa, 25 MPa, 28 MPa, 30 MPa, and any value within the range of any two values, preferably 20-30 MPa.

[0103] In some embodiments of the present invention, preferably, the adhesive layer has a bonding strength at -40°C ≥ 18 MPa, for example, 18 MPa, 20 MPa, 21 MPa, 22 MPa, 25 MPa, 28 MPa, 30 MPa, and any value within the range of any two values, preferably 20-30 MPa.

[0104] In some embodiments of the present invention, preferably, the elongation at 25°C of the adhesive layer is ≥200%, for example, 200%, 210%, 220%, 230%, 240%, 250%, 260%, 280%, 300%, and any value within the range of any two values, preferably 200-300%.

[0105] In some embodiments of the present invention, preferably, the elongation at -40°C of the adhesive layer is ≥40%, for example, 40%, 45%, 50%, 55%, 60%, 70%, and any value within the range of any two values, preferably 40-60%.

[0106] In this invention, unless otherwise specified, the bonding strength at -40℃ and the bonding strength at 25℃ are measured using GB / T 39289-2020 Determination of Adhesive Bonding Strength for Metals and Plastics; the elongation at -40℃ and the elongation at 25℃ are measured using GB / T 528-2009 Tensile Stress-Strain Properties of Vulcanized Rubber or Thermoplastic Rubber.

[0107] In some embodiments of the present invention, preferably, the adhesive layer is prepared by the following method: applying the adhesive to the lower side of the metal end cap and pressing it into the inner liner of the gas cylinder, so that the adhesive fills the contact surface between the metal end cap and the inner liner of the gas cylinder and is cured to obtain the adhesive layer.

[0108] One specific embodiment provided by the present invention is as follows: Figure 2-3 As shown, Figure 2 This is a schematic diagram of adhesive application. The metal end cap 1 is fixed on the base 2. The base 2 drives the metal end cap 1 to rotate slowly. The adhesive 7 is dripped onto the contact surface 4 (i.e., the contact surface 4 between the metal end cap 1 and the inner liner of the gas cylinder 3) through the flow delivery pump 6. The adhesive 7 is evenly applied to the contact surface 4 by the scraper 5. The scraper 5 and the contact surface 4 maintain a certain gap width to ensure the total amount of adhesive 4. At the same time, by setting the shape of the scraper 5, more adhesive is applied to the outer side than to the inner side. Figure 3 This is a schematic diagram of the formation of the adhesive layer. The metal end cap 1 coated with adhesive is pressed into the inner liner 3 of the gas cylinder through the pressing device 2, so that the adhesive and the inner liner 3 of the gas cylinder have good contact. During the pressing process, the outer adhesive can overflow through the contact surface 4 between the inner liner 3 of the gas cylinder and the metal end cap 1, forming an adhesive layer 8 to fill the gap between the two.

[0109] According to a particularly preferred embodiment of the present invention, an adhesive is prepared by reacting an adhesive composition, wherein the reaction conditions are: temperature of 60-90°C; rotation speed of 300-800 rpm; and time of 0.1-2 h.

[0110] The adhesive composition comprises: an epoxy ionic liquid resin having the structure shown in Formula I and / or Formula II, a vinyl ionic liquid resin having the structure shown in Formula III, a compound curing agent, and optionally an epoxy resin and / or a vinyl resin.

[0111]

[0112] Where m and n are each independently selected from integers 1-5; a and b are each independently selected from 1-5; x is selected from integers 1-5; y is selected from integers 0-5; L - Selected from NTf2 - Cl - OH- Ac - CN - HS - ;

[0113] The compound curing agent comprises: a first curing agent and a second curing agent, wherein the first curing agent is selected from amine curing agents or acid anhydride curing agents; and the second curing agent is selected from free radical initiators.

[0114] The mass ratio of the epoxy ionic liquid resin to the vinyl ionic liquid resin is 0.1-4:1; the mass ratio of the epoxy ionic liquid resin to the first curing agent is 1:0.2-1; and the mass ratio of the vinyl ionic liquid resin to the second curing agent is 1:0.001-0.01.

[0115] The present invention will be described in detail below through embodiments.

[0116] Example 1

[0117] 50g of epoxy ionic liquid resin (m=1, n=1, L selected from NTf2) having the structure shown in Formula I was used. - ), 50g of epoxy ionic liquid resin having the structure shown in Formula II (a=1, b=1, L selected from NTf2) - ), 50g of vinyl ionic liquid resin having the structure shown in Formula III (x = 1, y = 0, L selected from NTf2) - 25g of the first curing agent (4,4'-diaminodiphenyl ether) and 0.05g of the second curing agent (AIBN) were mixed and reacted at 80℃ and 500rpm for 1 hour to obtain adhesive S1.

[0118] Example 2

[0119] 5g of epoxy ionic liquid resin with the structure shown in Formula I (m=1, n=1, L selected from NTf2) was used. - ), 10g of epoxy-based ionic liquid resin having the structure shown in Formula II (a=1, b=1, L selected from NTf2) - ), 150g of vinyl ionic liquid resin having the structure shown in Formula III (x = 1, y = 0, L selected from NTf2) - 7.5g of the first curing agent (4,4'-diaminodiphenyl ether) and 1.5g of the second curing agent (AIBN) were mixed and reacted at 60℃ and 500rpm for 2 hours to obtain adhesive S2.

[0120] Example 3

[0121] 100g of epoxy ionic liquid resin (m=1, n=1, L selected from NTf2) having the structure shown in Formula I was used. -), 50g of epoxy ionic liquid resin having the structure shown in Formula II (a=1, b=1, L selected from NTf2) - ), 37.5g of vinyl ionic liquid resin having the structure shown in Formula III (x = 1, y = 0, L selected from NTf2) - 75g of the first curing agent (4,4'-diaminodiphenyl ether) and 0.375g of the second curing agent (AIBN) were mixed and reacted at 90℃ and 500rpm for 0.5h to obtain adhesive S3.

[0122] Example 4

[0123] The method is the same as in Example 1, except that...

[0124] 50g of epoxy ionic liquid resin (m=1, n=1, L selected from NTf2) having the structure shown in Formula I was used. - Replace with 40g of epoxy-based ionic liquid resin having the structure shown in Formula I (m=1, n=1, L selected from NTf2) - ) and 10g of diglycidyl adipic acid,

[0125] Under the same conditions, adhesive S4 was obtained.

[0126] Example 5

[0127] The method is the same as in Example 1, except that...

[0128] 50g of epoxy ionic liquid resin having the structure shown in Formula II (a=1, b=1, L selected from NTf2) was used. - Replace with 25g of epoxy-based ionic liquid resin having the structure shown in Formula II (a=1, b=1, L selected from NTf2) - ) and 25g of E51 type epoxy resin,

[0129] Under the same conditions, adhesive S5 was obtained.

[0130] Example 6

[0131] The method is the same as in Example 1, except that...

[0132] 50g of a vinyl ionic liquid resin having the structure shown in Formula III (x=1, y=0, L selected from NTf2) was used. - Replace with 20g of vinyl ionic liquid resin having the structure shown in Formula III (x = 1, y = 0, L selected from NTf2) - ) and 30g of 1-vinyl-3-methylimidazolium chloride,

[0133] Under the same conditions, adhesive S6 was obtained.

[0134] Example 7

[0135] The method is the same as in Example 1, except that...

[0136] 50g of epoxy ionic liquid resin (m=1, n=1, L selected from NTf2) having the structure shown in Formula I was used. - Replace with 45g of epoxy-based ionic liquid resin having the structure shown in Formula I (m=1, n=1, L selected from NTf2) - ) and 5g of adipic acid diglycidyl ester;

[0137] 50g of epoxy ionic liquid resin having the structure shown in Formula II (a=1, b=1, L selected from NTf2) was used. - Replace with 45g of epoxy-based ionic liquid resin having the structure shown in Formula II (a=1, b=1, L selected from NTf2) - ) and 5g E51 type epoxy resin;

[0138] 50g of a vinyl ionic liquid resin having the structure shown in Formula III (x=1, y=0, L selected from NTf2) was used. - Replace with 45g of vinyl ionic liquid resin having the structure shown in Formula III (x = 1, y = 0, L selected from NTf2) - ) and 5g of 1-vinyl-3-methylimidazolium chloride;

[0139] Under the same conditions, adhesive S7 was obtained.

[0140] Examples 8-13

[0141] The method is the same as in Example 1, except that...

[0142] By changing the type of ionic liquid resin, that is,

[0143] Example 8 replaces the structure shown in Equation I with m=1, n=2, and L selected from NTf2. - ;

[0144] Example 9 replaces the structure shown in Equation I with m=2, n=2, and L selected from NTf2. - ;

[0145] Example 10 replaces the structure shown in Equation II with a = 1, b = 6, and L selected from NTf2. - ;

[0146] Example 11 replaces the structure shown in Formula II with a = 1, b = 2, and L selected from OH. - ;

[0147] Example 12 replaces the structure shown in Equation III with x = 1, y = 1, and L selected from NTf2. - ;

[0148] Example 13 replaces the structure shown in Equation III with x = 1, y = 2, and L selected from OH. - ;

[0149] Under the same conditions, adhesives S8-S13 were obtained respectively.

[0150] Example 14

[0151] The method is the same as in Example 1, except that...

[0152] Change the type of ionic liquid resin, that is,

[0153] Replace the structure shown in Equation I with m = 2, n = 2, and L selected from OH. - Replace the structure shown in Equation II with a = 1, b = 2, and L selected from OH. - The structural formula III (x=1, y=1, L is selected from OH) is shown. - ;

[0154] Under the same conditions, adhesive S14 was obtained.

[0155] Comparative Example 1

[0156] The method is the same as in Example 1, except that...

[0157] Replace the imidazole ring in Formula I with a pyrrole ring;

[0158] Under the same conditions, adhesive DS1 was obtained.

[0159] Comparative Example 2

[0160] The method is the same as in Example 1, except that...

[0161] Replace the imidazole ring in Formula II with a pyridine ring;

[0162] Under the same conditions, adhesive DS2 was obtained.

[0163] Comparative Example 3

[0164] The method is the same as in Example 1, except that...

[0165] Replace the imidazole ring in Formula III with a pyrrole ring;

[0166] Under the same conditions, adhesive DS3 was obtained.

[0167] Comparative Example 4

[0168] The method is the same as in Example 1, except that...

[0169] Replace the imidazole ring in Formula III with a pyridine ring;

[0170] Under the same conditions, adhesive DS4 was obtained.

[0171] Test case

[0172] The adhesives prepared in the above examples and comparative examples were respectively coated on the lower side of the metal end cap, and then contacted with the winding resin that overflowed through the metal end cap and cured (temperature 120°C; time 2h) to obtain an adhesive layer of 0.1 mm. The physical properties of the adhesive layers are listed in Table 1.

[0173] Table 1

[0174]

[0175] As can be seen from the results in Table 1, compared with Comparative Examples 1-4, the adhesive layers prepared by the adhesive provided by the present invention in Examples 1-14 have good elongation, bonding strength and low temperature resistance, especially with high elongation at -40℃ and bonding strength at -40℃.

[0176] Comparative Examples 1-4 show that because pyrrole and pyridine lack active hydrogen to initiate epoxy ring opening, their low degree of crosslinking results in high elongation at break and low strength.

[0177] Compared to Example 1, Examples 4-7 respectively added vinyl resin and epoxy resin to regulate the degree of crosslinking of the adhesive, thereby affecting the performance of the adhesive layer. The main difference is that the performance is more affected at low temperatures and less affected at room temperature.

[0178] Compared to Example 1, Examples 8-14 caused performance fluctuations by adjusting the structure of the ionic liquid resin, specifically by adjusting the carbon chain length and anion changes of the ionic liquid resin, but its inherent properties ensured that its low-temperature performance remained good.

[0179] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An adhesive composition, characterized in that, The adhesive composition comprises: an epoxy-based ionic liquid resin having the structure shown in Formula I and / or Formula II, a vinyl-based ionic liquid resin having the structure shown in Formula III, and a compounded curing agent; Where m and n are each independently selected from integers 1-10; a and b are each independently selected from integers 1-10; x is selected from integers 1-10; y is selected from integers 0-10; L - Selected from anions.

2. The adhesive composition according to claim 1, wherein, The mass ratio of the epoxy ionic liquid resin to the vinyl ionic liquid resin is 0.1-10:1, preferably 0.1-4:1; Preferably, when the epoxy ionic liquid resin has the structures shown in Formula I and Formula II, the mass ratio of the compound shown in Formula I to the compound shown in Formula II is 0.1-5:1, preferably 0.5-2:

1.

3. The adhesive composition according to claim 1 or 2, wherein, L - Selected from NTf2 - Cl - I - ,Br - F - OH - Ac - CN - HS - , Preferred from NTf2 - Cl - OH - Ac - CN - HS - More preferably selected from NTf2 - Cl - ; Preferably, in Formula I, m and n are each independently selected from integers from 1 to 5; Preferably, in Formula II, a and b are each independently selected from integers from 1 to 5; Preferably, in Formula III, x is selected from integers from 1 to 5, and y is selected from integers from 0 to 5.

4. The adhesive composition according to any one of claims 1-3, wherein, The compound curing agent includes: a first curing agent and a second curing agent, wherein the first curing agent is selected from amine curing agents or acid anhydride curing agents; and the second curing agent is selected from free radical initiators. Preferably, the mass ratio of the epoxy-based ionic liquid resin to the first curing agent is 1:0.1-4, more preferably 1:0.1-2, and even more preferably 1:0.2-1; Preferably, the mass ratio of the vinyl ionic liquid resin and the second curing agent is 1:0.001-0.04, more preferably 1:0.001-0.02, and even more preferably 1:0.001-0.

01.

5. The adhesive composition according to claim 4, wherein, The amine curing agent is selected from diamine curing agents, preferably from at least one of isophorone diamine, 4,4'-diaminodiphenyl ether, hydroxyethyl ethylenediamine, diethylenetriamine, aminoethylpiperazine, 1,2-diaminocyclohexane and methylenebicyclohexaneamine; Preferably, the anhydride curing agent is selected from diacid anhydride curing agents, and more preferably from at least one of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride and methylnadic anhydride; Preferably, the free radical initiator is selected from at least one of sodium persulfate, potassium persulfate, azobisisobutyronitrile, azobisisoheptanenitrile, dimethyl azobisisobutyrate, peroxybenzoic acid, peroxymethyl ethyl ketone, benzoyl peroxide, and cyclohexanone peroxide.

6. The adhesive composition according to any one of claims 1-5, wherein, The adhesive composition further includes: epoxy resin and / or vinyl resin; Preferably, when the adhesive composition further includes epoxy resin, the mass ratio of the epoxy-based ionic liquid resin to the epoxy resin is 1:0.1-5, preferably 1:0.1-2; or, When the adhesive composition further includes a vinyl resin, the mass ratio of the epoxy ionic liquid resin to the vinyl resin is 1:0.1-2, preferably 1:0.5-1; or, When the adhesive composition further includes epoxy resin and vinyl resin, the mass ratio of the epoxy ionic liquid resin, epoxy resin and vinyl resin is 1:0.1-5:0.1-2, preferably 1:0.1-2:0.5-1; Preferably, the adhesive composition comprises an epoxy-based ionic liquid resin having the structure shown in Formula I and / or Formula II, a vinyl-based ionic liquid resin having the structure shown in Formula III, and a compounded curing agent; Alternatively, the adhesive composition comprises an epoxy ionic liquid resin having the structure shown in Formula I and / or Formula II, a vinyl ionic liquid resin having the structure shown in Formula III, a compound curing agent, an epoxy resin, and / or a vinyl resin; Preferably, the epoxy resin is selected from at least one of the following: diglycidyl phthalate, E51 type epoxy resin, E44 type epoxy resin, triglycidyl m-aminophenol, tetraglycidyl diaminodiphenylmethane, diglycidyl p-aminophenol, 3-ESL aminomethylcyclohexane, diglycidyl hexahydrophthalic acid, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl tetrahydrophthalic acid, diglycidyl methyltetrahydrophthalic acid, and diglycidyl methylenetetrahydrophthalic acid. Preferably, the vinyl resin is selected from at least one of 1-vinyl-3-methylimidazolium chloride, bisphenol A epoxy vinyl ester, methyl methacrylate, glycidyl methacrylate, and glycidyl acrylate.

7. An adhesive, characterized in that, The adhesive is prepared by reaction from the adhesive composition according to any one of claims 1-6; The reaction conditions are as follows: temperature is 10-130℃, preferably 60-90℃; rotation speed is 100-1000rpm, preferably 300-800rpm; and time is 0.1-5h, preferably 0.1-2h.

8. The application of the adhesive of claim 7 in a plastic liner, preferably in a carbon fiber wound hydrogen storage cylinder with a plastic liner.

9. A composite component, characterized in that, The composite component includes a metal end cap disposed on the top and a gas cylinder liner disposed on the bottom, as well as an adhesive layer disposed between the metal end cap and the gas cylinder liner; The adhesive layer is obtained by curing the adhesive described in claim 7.

10. The composite component according to claim 9, wherein, The curing conditions are: temperature of 10-130℃, preferably 60-90℃; time of 0.1-5h, preferably 0.1-2h. Preferably, the adhesive layer has an adhesive strength of -40°C and an adhesive strength of 25°C that are each ≥18MPa, and more preferably 20-30MPa. Preferably, the elongation at -40°C of the adhesive layer is ≥40%, more preferably 40-70%; and the elongation at 25°C is ≥200%, more preferably 200-300%. Preferably, the adhesive layer is prepared by the following method: applying the adhesive to the lower side of the metal end cap and pressing it into the inner liner of the gas cylinder, so that the adhesive fills the contact surface between the metal end cap and the inner liner of the gas cylinder and is cured to obtain the adhesive layer.

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