Ternary copolymer tape type dry-wet dual-purpose adhesive, preparation method and use thereof

Abstract

The application provides a ternary copolymer adhesive tape type dry-wet dual-purpose adhesive and a preparation method and application thereof, and relates to the material field. The ternary copolymer adhesive tape type dry-wet dual-purpose adhesive is obtained by radical polymerization of raw materials including benzyl acrylate, trimethylacryloyloxyethyl ammonium bis-trifluoromethane sulfonimide, poly(ethylene glycol) methyl ether acrylate and an initiator. The preparation method comprises the following steps: mixing the raw materials to obtain a precursor solution, and then performing polymerization to obtain the ternary copolymer adhesive tape type dry-wet dual-purpose adhesive. The application of the ternary copolymer adhesive tape type dry-wet dual-purpose adhesive is used for air and underwater bonding. The ternary copolymer adhesive tape type dry-wet dual-purpose adhesive provided by the application has simple preparation raw materials, does not need to use a synthetic complex catechol functional group-containing monomer material, has a simple preparation process, and can realize instant strong adhesion to the surfaces of plastic substrates such as PET, PMMA and PTFE in air and underwater.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of materials, in particular to a ternary copolymer tape type dry-wet adhesive, a preparation method and use thereof. BACKGROUND

[0002] Adhesives are widely used in our daily life and industrial production, such as sticky notes and adhesive bandages. Balancing interfacial adhesion and bulk strength is the key to achieving high adhesion. Most commercial adhesives are liquid materials, which have excellent wettability and weak cohesive strength before use; when used, the liquid adhesive fully contacts the substrate and solidifies to form a solid material with strong cohesive strength, which can bond the adherends together. Most commercial adhesives can achieve efficient and long-lasting bonding in dry environments, such as 502 glue. However, it is difficult and challenging to achieve bonding between the adhesive and the substrate surface in underwater environments. This is because the hydration layer formed on the substrate surface blocks its effective contact with the adhesive, making it difficult for the two to interact at the molecular level; in addition, water tends to be trapped in the adhesive interface, reducing the contact area between the two from a macroscopic perspective, making it difficult for the interface to adhere. In fact, in many applications, adhesives are required to contact non-dry surfaces or be immersed in water-based media to bond with the substrate, such as implantable medical devices, wound dressings, water-based energy devices, underwater sensors, underwater repairs, and marine industries. Therefore, developing adhesives that can be used in various underwater environments to meet different application scenarios has gradually become a new research hotspot.

[0003] Removing the hydration layer is crucial for underwater adhesion. It can be achieved by absorbing or excluding water. Materials based on the absorption principle to remove water layer are mostly gel materials, including hydrogels and organic gels. However, gel-based adhesives have the problem of unstable performance due to evaporation or leakage of liquid. Adhesives based on the hydrophobic principle to exclude water layer are generally achieved by hydrophobic components, and the materials are mostly polymer materials without liquid or with high-boiling ionic liquids, which can avoid the concern of performance instability due to the loss of liquid components, and have higher storage stability than gel-based adhesives. Currently, more research introduces o-diphenol as a side chain to prepare underwater adhesives. The o-diphenol has the characteristics of hydrophobic benzene ring and hydrophilic hydroxyl group, which makes the material have good adhesion effect, but it has the problem of easy oxidation to quinone structure, which leads to performance decline or even failure, and the preparation cost is relatively high.

[0004] According to different bonding modes, adhesives can be roughly divided into glue type and tape type. The glue type adhesive is usually composed of polymerizable or crosslinkable monomers or oligomers, and the interface interaction at the molecular level occurs during the underwater curing process. Subsequently, the liquid forms a solid through polymerization / crosslinking. The glue type adhesive generally has good interface bonding strength due to its high surface wettability to the substrate, but it needs additional curing time when used and cannot be reused after curing, and it is easy to leave residual glue when debonding. In contrast, the tape type adhesive is made of a polymer with low modulus, and underwater adhesion is mainly achieved through intermolecular interaction, with the characteristics of instantaneous adhesion and reusability. However, the tape type adhesive has lower surface wettability to the substrate than the glue type adhesive, which can easily lead to interface bonding failure. Therefore, the research and development of glue type adhesives focuses on the design of their chemical structure to ensure strong cohesion, while the design of tape type adhesives focuses more on breaking the hydration layer of the substrate surface and achieving strong interaction with the substrate. SUMMARY

[0005] The purpose of the present application is to provide a ternary copolymer tape type dry and wet dual-purpose adhesive and its preparation method and use, in order to solve the above problems.

[0006] To achieve the above purpose, the following technical solutions are adopted in the present application:

[0007] A ternary copolymer tape type dry and wet dual-purpose adhesive is obtained by free radical polymerization of raw materials including benzyl acrylate, trimethylacryloyloxyethylammonium bis-trifluoromethanesulfonimide, poly(ethylene glycol) methyl ether acrylate and an initiator.

[0008] The present application also provides a preparation method of the ternary copolymer tape type dry and wet dual-purpose adhesive, comprising:

[0009] The raw materials are mixed to obtain a precursor solution, and then a polymerization reaction is carried out to obtain the ternary copolymer tape type underwater adhesive.

[0010] Preferably, the molecular weight of the poly(ethylene glycol) methyl ether acrylate is less than or equal to 1000.

[0011] Preferably, the initiator includes a photoinitiator or a thermal initiator.

[0012] The photoinitiator includes one or more of 2,2-diethoxyacetophenone, benzophenone, Irgacure 184 and Irgacure 819, and the thermal initiator includes 2,2-azobisisobutyronitrile and / or benzoyl peroxide.

[0013] Preferably, the molar ratio of benzyl acrylate to trimethylacryloyloxyethylammonium bis-trifluoromethanesulfonimide is (1-4): 1.

[0014] Preferably, the ratio of the total moles of the poly(ethylene glycol) methyl ether acrylate, the benzyl acrylate and the trimethylammonium ethyl (meth)acrylate methylsulfate is (0.1-0.3):1.

[0015] Preferably, the ratio of the total moles of the initiator, the benzyl acrylate, the trimethylammonium ethyl (meth)acrylate methylsulfate and the poly(ethylene glycol) methyl ether acrylate is 0.005-0.02:1.

[0016] Preferably, the polymerization reaction is carried out at room temperature for 0.5-4h, or at 60-70℃ for 8-12h.

[0017] Preferably, the polymerization reaction is carried out in a mold.

[0018] The mold comprises an upper substrate, a PET release film, a gasket, a PET general film and a lower substrate which are sequentially stacked, and the PET release film, the gasket and the PET general film form a containing space for containing the precursor solution.

[0019] The application also provides a use of the ternary copolymer adhesive tape type dry-wet dual-purpose adhesive for bonding in air and underwater.

[0020] Compared with the prior art, the application has the following beneficial effects:

[0021] The ternary copolymer adhesive tape type dry-wet dual-purpose adhesive provided by the application uses benzyl acrylate, trimethyl methacryloyloxyethyl ammonium bis-trifluoromethane sulfonimide, and poly(ethylene glycol) methyl ether acrylate as monomers, does not need to use a synthetic complex catechol functional group-containing monomer material, and can realize instant strong adhesion to the surfaces of plastic substrates such as PET, PMMA, and PTFE in air and underwater. The ternary copolymer adhesive tape type dry-wet dual-purpose adhesive can form hydrogen bonds, π-π interactions, cation-π interactions, and hydrophobic interactions between the adhesive and the adherend, can maintain good wetting of the plastic substrate and form strong adhesion under water. Taking a PET substrate as an example, 90° peeling tests show that the underwater adhesive prepared by adhesion in air or water can produce adhesion of about 1100 N / m to the substrate. In addition, the adhesive also has good adaptability to acid-base environments and high-salinity environments. The adhesive can still produce strong adhesion of 955, 968, and 948 N / m to the PET substrate in a pH = 3, pH = 11, and artificial seawater environment. At the same time, the ternary copolymer adhesive tape type dry-wet dual-purpose adhesive also has good mechanical properties. Tensile tests show that the copolymer can be stretched by nearly 14 times and reach a strength of 0.38 MPa, indicating that the adhesive not only has high adhesion but also has good cohesion, and thus can realize the effect of repeatable adhesion. Tests show that for a PET substrate, after 10 adhesion and peeling cycles, the adhesive force to the substrate can still reach nearly 1100 N / mm. The dry-wet dual-purpose adhesive has long-term storage stability and does not change in adhesion force after being placed in an environmental condition for several months.

[0022] The preparation method of the ternary copolymer adhesive tape type dry-wet dual-purpose adhesive provided by the application is simple.

[0023] The ternary copolymer adhesive tape type dry-wet dual-purpose adhesive provided by the application can be widely used for adhesion in air and underwater. BRIEF DESCRIPTION OF DRAWINGS

[0024] In order to more clearly illustrate the technical solutions of the embodiments of the application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some embodiments of the application, and therefore should not be regarded as a limitation on the scope of the application.

[0025] Figure 1 A schematic diagram of a mold used for the embodiments;

[0026] Figure 2 A 90° peeling photo of the adhesion of the embodiments to a PET substrate. DETAILED DESCRIPTION

[0027] As used herein:

[0028] "comprising," "having," "including," "containing," "characterized by" or any other variation thereof is intended to cover non-exclusive inclusion, such that a composition, step, method, article, or apparatus that comprises, has, includes, contains, characterizes, or is characterized by a list of elements can include other elements not expressly listed or inherent to such composition, step, method, article, or apparatus. "Consisting essentially of, when

[0029] The conjunctive term "consisting of' excludes any element, step, or ingredient not specified. If used in the claims, this phrase shall

[0030] When expressing a range of equivalents, concentrations, or other values or parameters as a range, preferably a range of upper and lower preferred values, it is to be understood that the disclosure is specifically intended to embrace all ranges formed by any pair of any stated upper and lower values, regardless of whether such ranges are expressly stated or not. For example, where a range of "1 to 5" is disclosed, the disclosure is to be interpreted to include ranges of "1 to 4," "1 to 3," "1 to 2," "1 to 2 and 4 to 5," "1 to 3 and 5," etc. Where a range of values is described herein, it is intended to encompass all integer and fraction values within that range, unless otherwise indicated.

[0031] In these embodiments, the parts and percentages described are by mass, unless otherwise indicated.

[0032] "Parts by mass" refers to a basic unit of measurement that represents the proportional relationship of the mass of multiple components, 1 part can represent any unit mass, such as 1 g, 2.689 g, etc. If we say that the mass of component A is a parts and the mass of component B is b parts, it means that the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it means that the mass of component A is aK and the mass of component B is bK (K is an arbitrary number, representing a multiple factor). It must not be misunderstood that, unlike parts by mass, the sum of the parts by mass of all components is not limited to 100 parts.

[0033] "and / or" is used to indicate one or both of the stated circumstances can occur, for example, A and / or B includes (A and B) and (A or B).

[0034] A ternary copolymer tape type dry-wet dual-purpose adhesive is prepared by free radical polymerization of raw materials including benzyl acrylate, trimethylacryloyloxyethylammonium bis-trifluoromethanesulfonimide, poly(ethylene glycol) methyl ether acrylate and an initiator.

[0035] The structural formulas of the three monomers are shown as follows:

[0036]

[0037] The structural formulas of benzyl acrylate (BzA), trimethylacryloyloxyethylammonium bis-trifluoromethanesulfonimide (AETATFSI) and poly(ethylene glycol) methyl ether acrylate (OEGA) correspond to (a), (b) and (c) respectively, and the monomers are randomly arranged after copolymerization.

[0038] The application also provides a preparation method of the ternary copolymer tape type dry-wet dual-purpose adhesive, comprising:

[0039] The raw materials are mixed to obtain a precursor solution, and then a polymerization reaction is performed to obtain a ternary random copolymer tape type underwater adhesive.

[0040] In an optional embodiment, the molecular weight of the poly(ethylene glycol) methyl ether acrylate is less than or equal to 1000 to avoid polymer crystallization.

[0041] In an optional embodiment, the initiator includes a photoinitiator or a thermal initiator.

[0042] The photoinitiator includes one or more of 2,2-diethoxyacetophenone, benzophenone, Irgacure 184 and Irgacure 819, and the thermal initiator includes 2,2-azobisisobutyronitrile and / or benzoyl peroxide.

[0043] In an optional embodiment, the molar ratio of the benzyl acrylate to the trimethylacryloyloxyethylammonium bis-trifluoromethanesulfonimide is (1-4):1.

[0044] Alternatively, the molar ratio of the benzyl acrylate to the trimethylacryloyloxyethylammonium bis-trifluoromethanesulfonimide can be 1:1, 2:1, 3:1, 4:1 or any value between 1 and 4.

[0045] In an optional embodiment, the ratio of the poly(ethylene glycol) methyl ether acrylate to the total molar amount of the benzyl acrylate and the trimethylacryloyloxyethylammonium bis-trifluoromethanesulfonimide is (0.1-0.3):1.

[0046] Optionally, the ratio of the amount of the initiator to the total moles of the benzyl acrylate, the trimethylammonium ethyl methacrylate bis-trifluoromethanesulfonimide, and the poly(ethylene glycol) methyl ether acrylate can be 0.005:1, 0.01:1, 0.015:1, 0.02:1, or any value between 0.005-0.02:1.

[0047] In an optional embodiment, the ratio of the amount of the initiator to the total moles of the benzyl acrylate, the trimethylammonium ethyl methacrylate bis-trifluoromethanesulfonimide, and the poly(ethylene glycol) methyl ether acrylate is 0.005-0.02:1.

[0048] In an optional embodiment, the ratio of the amount of the initiator to the total moles of the benzyl acrylate, the trimethylammonium ethyl methacrylate bis-trifluoromethanesulfonimide, and the poly(ethylene glycol) methyl ether acrylate can be 0.005:1, 0.01:1, 0.015:1, 0.02:1, or any value between 0.005-0.02:1.

[0049] In an optional embodiment, the polymerization reaction is carried out at room temperature for 0.5-4h or at 60-70℃ for 8-12h.

[0050] In an optional embodiment, the polymerization reaction is carried out at room temperature for 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, or any value between 0.5-4h; or at 60℃, 61℃, 62℃, 63℃, 64℃, 65℃, 66℃, 67℃, 68℃, 69℃, 70℃, or any value between 60-70℃ for 8h, 9h, 10h, 11h, 12h, or any value between 8-12h.

[0051] In an optional embodiment, the polymerization reaction is carried out in a mold;

[0052] The mold comprises an upper substrate, a PET release film, a gasket, a PET general film, and a lower substrate arranged in sequence, and the PET release film, the gasket, and the PET general film form a containing space for containing the precursor solution.

[0053] The application also provides a use of the ternary copolymer adhesive tape type dry-wet dual-purpose adhesive, which is mainly used for underwater bonding and can also be used for bonding in air.

[0054] The embodiments of the present application will be described in detail below with specific examples, but those skilled in the art will understand that the following examples are only for illustration of the present application and should not be regarded as limiting the scope of the present application. The specific conditions are not specified in the examples, and the conventional conditions or the conditions recommended by the manufacturer are used. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be obtained by commercial purchase.

[0055] First, the mold used in the embodiments of the present application will be described.

[0056] As shown in Figure 1 , the mold includes an upper substrate, a PET release film, a gasket, a PET general film, and a lower substrate which are sequentially stacked. The upper substrate and the lower substrate are both glass, and the gasket is a silica gel material in the shape of a square box with a thickness of 0.2-1.5 mm. The PET release film, the gasket, and the PET general film form a containing space for containing the precursor solution.

[0057] Example 1

[0058] This embodiment provides a ternary copolymer adhesive tape type wet and dry adhesive, and the preparation method is as follows:

[0059] (1) Mix monomer I benzyl acrylate (BzA), monomer II trimethylacryloyloxyethyl ammonium bis-trifluoromethanesulfonimide (AETATFSI), and monomer III poly(ethylene glycol) methyl ether acrylate (OEGA), and add reagent IV 2,2-diethoxyphenylethanone, and mix thoroughly;

[0060] The molar ratio of monomer I to monomer II is 4:1; the amount of monomer III is 0.1 molar ratio of the total amount of monomer I and monomer II; and the molar ratio of reagent IV is 0.01 of the total amount of monomer I, monomer II, and monomer III.

[0061] (2) Place the PET release film and the general PET film on both sides of the gasket, and then place the glass sheet. After clamping, the mold is obtained;

[0062] (3) Inject the precursor solution obtained in step (1) into the mold of step (2), and perform polymerization reaction under 8W ultraviolet lamp for 2h;

[0063] (4) After the reaction is completed, the material and the PET film are connected together and taken out to obtain a ternary copolymer adhesive tape type underwater adhesive.

[0064] The 90° peeling photograph of the obtained ternary copolymer adhesive tape type underwater adhesive adhering to the PET substrate is shown in Figure 2 .

[0065] Example 2

[0066] The embodiment provides a ternary copolymer adhesive tape type dry-wet adhesive, and a preparation method thereof is as follows:

[0067] (1) monomer I benzyl acrylate (BzA), monomer II trimethyl acryloyloxyethyl ammonium bis-trifluoromethanesulfonimide (AETATFSI) and monomer III poly(ethylene glycol) methyl ether acrylate (OEGA) are mixed, reagent IV 2,2-diethoxyacetophenone is added, and uniform mixing is performed;

[0068] The molar ratio of monomer I to monomer II is 2:1; the amount of monomer III is 0.1 molar ratio of the total amount of monomer I and monomer II; and the molar ratio of reagent IV to the total amount of monomer I, monomer II and monomer III is 0.01.

[0069] (2) PET release film and ordinary PET film are placed on both sides of a gasket, and a glass sheet is placed, so that a mold is obtained after clamping;

[0070] (3) the precursor solution obtained in step (1) is injected into the mold in step (2), and polymerization reaction is carried out under 36W ultraviolet light for 1h;

[0071] (4) after the reaction is completed, the material and the PET film are connected together and taken out, and a ternary copolymer adhesive tape type underwater adhesive is obtained.

[0072] Example 3

[0073] The embodiment provides a ternary copolymer adhesive tape type dry-wet adhesive, and a preparation method thereof is as follows:

[0074] (1) monomer I benzyl acrylate (BzA), monomer II trimethyl acryloyloxyethyl ammonium bis-trifluoromethanesulfonimide (AETATFSI) and monomer III poly(ethylene glycol) methyl ether acrylate (OEGA) are mixed, reagent IV 2,2-diethoxyacetophenone is added, and uniform mixing is performed;

[0075] The molar ratio of monomer I to monomer II is 1:1; the amount of monomer III is 0.15 molar ratio of the total amount of monomer I and monomer II; and the molar ratio of reagent IV to the total amount of monomer I, monomer II and monomer III is 0.01.

[0076] (2) PET release film and ordinary PET film are placed on both sides of a gasket, and a glass sheet is placed, so that a mold is obtained after clamping;

[0077] (3) the precursor solution obtained in step (1) is injected into the mold in step (2), and polymerization reaction is carried out under 100W ultraviolet light for 0.5h;

[0078] (4) after the reaction is completed, the material and the PET film are connected together and taken out, and a ternary copolymer adhesive tape type underwater adhesive is obtained.

[0079] Comparative Example 1

[0080] Binary copolymer 1

[0081] (1) Benzyl acrylate (BzA) as monomer I and trimethylacryloyloxyethyl ammonium bis-trifluoromethanesulfonimide (AETATFSI) as monomer II were mixed, and reagent IV 2,2-diethoxyacetophenone was added and mixed uniformly;

[0082] The molar ratio of monomer I to monomer II was 3:2; the molar ratio of reagent IV was 0.03 of the total amount of monomer I and monomer II.

[0083] (2) The PET release film and the ordinary PET film were placed on both sides of the gasket, and then the glass sheet was placed, and the mold was obtained after clamping;

[0084] (3) The precursor solution obtained in step (1) was injected into the mold of step (2), and the polymerization reaction was carried out under 8W ultraviolet light for 4h;

[0085] (4) After the reaction was completed, the material and the PET film were taken out together to obtain the binary copolymer adhesive tape type adhesive.

[0086] The Young's modulus of the obtained binary copolymer adhesive tape type adhesive was about 600MPa, the wettability on the adherend surface was poor, and the adhesion force on the PET substrate was not generated in the air or underwater.

[0087] Comparative Example 2

[0088] Binary copolymer 2

[0089] (1) Benzyl acrylate (BzA) as monomer I and poly(ethylene glycol) methyl ether acrylate (OEGA) as monomer III were mixed, and reagent IV 2,2-diethoxyacetophenone was added and mixed uniformly;

[0090] The amount of monomer III was 0.15 molar ratio of monomer I; the molar ratio of reagent IV was 0.01 of monomer I.

[0091] (2) The PET release film and the ordinary PET film were placed on both sides of the gasket, and then the glass sheet was placed, and the mold was obtained after clamping;

[0092] (3) The precursor solution obtained in step (1) was injected into the mold of step (2), and the polymerization reaction was carried out under 8W ultraviolet light for 2h;

[0093] (4) After the reaction was completed, the material and the PET film were taken out together to obtain the binary copolymer adhesive tape type adhesive.

[0094] The obtained binary copolymer tape type adhesive does not contain cation-π interaction, and the adhesion force generated by the adhesion of the adhesive to the PET substrate in air or underwater is 454 N / m, which is lower than that of the proposed ternary copolymer tape type adhesive.

[0095] It should be noted that the adhesion force is characterized by using 90° peeling test, and the calculation method is force divided by tape width.

[0096] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not limited thereto; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

[0097] In addition, those skilled in the art can understand that although some embodiments herein include certain features included in other embodiments rather than other features, the combination of features of different embodiments means that it is within the scope of the present application and forms different embodiments. For example, in the above claims, any one of the claimed embodiments can be used in any combination. The information disclosed in the background section is only intended to deepen the understanding of the overall background of the present application, and should not be regarded as acknowledging or implying in any form that the information constitutes prior art known to those skilled in the art.

Claims

1. The use of a terpolymer tape-type wet / dry adhesive, characterized in that, For bonding in air and underwater; The terpolymer tape-type wet and dry adhesive is obtained by free radical polymerization of raw materials including benzyl acrylate, trimethacryloyloxyethylammonium bis(trifluoromethanesulfonylimide), poly(ethylene glycol) methyl ether acrylate and an initiator. The preparation method of the terpolymer tape-type wet and dry adhesive includes: The raw materials are mixed to obtain a precursor liquid, and then a polymerization reaction is carried out to obtain the terpolymer tape-type wet and dry adhesive. The molecular weight of the poly(ethylene glycol) methyl ether acrylate is less than or equal to 1000.

2. The use according to claim 1, characterized in that, The initiator includes a photoinitiator or a thermal initiator; The photoinitiator includes one or more of 2,2-diethoxyacetophenone, benzophenone, Irgacure 184, and Irgacure 819, and the thermal initiator includes 2,2-azobisisobutyronitrile and / or benzoyl peroxide.

3. The use according to claim 1, characterized in that, The molar ratio of benzyl acrylate to trimethylacryloyloxyethylammonium bis(trifluoromethanesulfonyl)imide is (1-4):

1.

4. The use according to claim 1, characterized in that, The total molar ratio of the poly(ethylene glycol) methyl ether acrylate to the benzyl acrylate and the trimethylacryloyloxyethylammonium bis(trifluoromethanesulfonylimide) is (0.1-0.3):

1.

5. The use according to claim 1, characterized in that, The ratio of the amount of the initiator to the total molar amount of the benzyl acrylate, the trimethacryloyloxyethylammonium bis(trifluoromethanesulfonyl)imide, and the poly(ethylene glycol) methyl ether acrylate is 0.005-0.02:

1.

6. The use according to claim 1, characterized in that, The polymerization reaction is carried out at room temperature for 0.5-4 hours, or at 60-70°C for 8-12 hours.

7. The use according to any one of claims 1-6, characterized in that, The polymerization reaction is carried out in a mold; The mold includes an upper substrate, a PET release film, a gasket, a PET ordinary film, and a lower substrate stacked in sequence. The PET release film, the gasket, and the PET ordinary film form a containment space for containing the precursor liquid.

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