An electrically conductive reduced tack adhesive tape resistant to plasticizer extraction and method of making same

Abstract

The application belongs to the technical field of adhesive materials, and particularly relates to an anti-plasticizer-outcoming power-on adhesion-reducing adhesive tape and a preparation method thereof. The application provides a preparation method of the anti-plasticizer-outcoming power-on adhesion-reducing adhesive tape, which comprises the following steps: S1, stirring and mixing 30-40 parts of modified polyethylene glycol diacrylate, 30-40 parts of polyurethane acrylate, 4-8 parts of montmorillonite, 2-4 parts of 2-hydroxy-2-methylpropiophenone, 1-3 parts of a plasticizer and 1-3 parts of an antioxidant to obtain a mixture; S2, coating the mixture on a release film by using a doctor blade coater, UV curing for 60-80 s to obtain an adhesive layer, and then attaching a protective film to the adhesive layer to obtain the anti-plasticizer-outcoming power-on adhesion-reducing adhesive tape. The adhesive tape has good power-on adhesion-reducing effect, and can avoid the occurrence of residual glue after power-on.

Description

Technical Field

[0001] This invention belongs to the field of adhesive materials technology, specifically relating to an anti-plasticizer precipitation electrically conductive anti-tack tape and its preparation method. Background Technology

[0002] In many areas of industrial production, material adhesion has always been a key factor affecting production efficiency, product quality, and equipment operational stability. Traditional methods for solving material adhesion and high viscosity problems have many limitations. For example, chemical additives may introduce impurities that affect product quality, and physical methods such as mechanical stirring are energy-intensive and have limited effectiveness. Electro-viscosity reduction technology, as an emerging viscosity reduction method, has unique advantages. Based on the influence of an electric field on the molecular structure or interaction of substances, it achieves viscosity control without introducing additional chemical substances, and is characterized by being green, environmentally friendly, and energy-efficient, providing a new and effective way to solve problems such as material adhesion and energy consumption reduction. The research and application of electro-viscosity reduction technology has shown a continuous development trend globally. Since the concept of this technology was proposed, many research institutions and enterprises have actively invested in research and development, achieving a series of important advances. At the basic research level, the exploration of the mechanism of action of electro-viscosity reduction technology has been continuously deepened, revealing the microscopic process of the interaction between the electric field and the material from the perspectives of molecular dynamics, colloid chemistry, and other disciplines, providing a solid theoretical foundation for technology optimization. In the application field, electro-viscosity reduction technology has been practiced in many industries.

[0003] Electrostatically conductive adhesive tape is a smart material that dynamically changes its adhesive force through electric field modulation. Its core mechanism involves triggering a physical or chemical reaction within the material after an electric current is applied, significantly reducing its stickiness and enabling non-destructive disassembly and reuse. Electrostatically conductive adhesive tape and related products are gaining popularity. As electronic products become increasingly thinner and miniaturized, numerous companies have developed various new types of electrostatically conductive adhesive tapes for fixing electronic components. When repairing or replacing components, the electrostatically conductive adhesive allows for easy disassembly, preventing damage to the components and meeting the needs of electronic product production and maintenance.

[0004] Chinese patent (publication number CN119193019B) discloses an electrically conductive and non-sticky adhesive tape, its preparation method, and its application. This invention involves mixing and stirring an acrylic pressure-sensitive adhesive, a UV prepolymer, a composite conductive hydrogel, a curing agent, a photoinitiator, a solvent, and a leveling agent to obtain a conductive adhesive. The conductive adhesive is then coated onto the upper and lower surfaces of an aluminum foil substrate and dried at 80-100℃ for 5-6 minutes to obtain a conductive adhesive layer. A release film is then bonded to the upper and lower surfaces of the conductive adhesive layer to obtain the electrically conductive and non-sticky tape. However, this patented technology requires the addition of modified inorganic conductive fillers to effectively achieve electrical conductivity and non-stickiness. The modification process for inorganic conductive fillers is complex, and research on the issue of plasticizer precipitation in the tape is lacking.

[0005] Therefore, how to design the components of electrically conductive anti-tack tape to avoid plasticizer precipitation during use, while achieving good anti-tack effect and avoiding residue after energization, has become a research direction. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide an anti-plasticizer leaching adhesive tape and its preparation method. The present invention uses polyethylene glycol diacrylate and 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as raw materials to prepare modified polyethylene glycol diacrylate. This is combined with cationic polyurethane acrylate, humic acid / montmorillonite complex, 2-hydroxy-2-methylphenylacetone, plasticizer, and oxidant to prepare the anti-plasticizer adhesive tape. The humic acid / montmorillonite complex adsorbs the plasticizer diisobutyl phthalate to prevent leaching, while the dissociable anionic and cationic groups achieve anti-adhesion through electrolysis, effectively avoiding residual adhesive after electrolysis.

[0007] A first aspect of the present invention provides a method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape, comprising the following steps:

[0008] S1. By weight, 30-40 parts of modified polyethylene glycol diacrylate, 30-40 parts of polyurethane acrylate, 4-8 parts of montmorillonite, 2-4 parts of 2-hydroxy-2-methylphenylacetone, 1-3 parts of plasticizer and 1-3 parts of antioxidant are stirred and mixed to obtain a mixture.

[0009] S2. Apply the mixture onto a release film using a doctor blade coater, and UV cure for 60-80 seconds to obtain an adhesive layer. Then, attach a protective film to the adhesive layer to obtain an anti-plasticizer exudation, electrically conductive, and non-sticky tape.

[0010] As a preferred embodiment of the present invention, the modified polyethylene glycol diacrylate may be present in weight parts of 30, 32, 34, 36, 38, or 40 parts, etc.

[0011] As a preferred embodiment of the present invention, the polyurethane acrylate may be expressed in parts by weight of 30, 32, 34, 36, 38, or 40 parts, etc.

[0012] As a preferred embodiment of the present invention, the weight parts of the montmorillonite can be 4 parts, 5 parts, 34 parts, 6 parts, 7 parts, or 8 parts, etc.

[0013] As a preferred embodiment of the present invention, the weight parts of the 2-hydroxy-2-methylphenylacetone may be 2 parts, 2.5 parts, 3 parts, 3.5 parts, or 4 parts, etc.

[0014] As a preferred embodiment of the present invention, the plasticizer may be present in parts by weight of 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts, etc.

[0015] As a preferred embodiment of the present invention, the antioxidant may be present in parts by weight of 1 part, 1.5 parts, 2 parts, 2.5 parts, or 3 parts, etc.

[0016] As a preferred technical solution of the present invention, the preparation method of the modified polyethylene glycol diacrylate includes: using commercially available polyethylene glycol diacrylate and 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as raw materials, a polymerization reaction is carried out under the action of azobisisobutyronitrile to obtain modified polyethylene glycol diacrylate.

[0017] This invention uses polyethylene glycol diacrylate and 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as raw materials. The polyethylene glycol diacrylate molecule has an acrylate group at each end, which can undergo free radical polymerization. 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide is an ionic liquid monomer with an allyl functional group. Azobisisobutyronitrile is used as an initiator. When heated, it decomposes to generate free radicals, which initiate the polymerization of the double bond between the acrylate group and the allyl functional group, thereby preparing modified polyethylene glycol diacrylate.

[0018] As a preferred embodiment of the present invention, the polymerization reaction steps are as follows: by weight, 1-3 parts of 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 10-20 parts of commercially available polyethylene glycol diacrylate and 0.3-0.5 parts of azobisisobutyronitrile are added to 100-120 parts of anhydrous ethanol and stirred and mixed, and polymerized at 50-60°C for 10-12 hours under a nitrogen atmosphere, followed by vacuum drying.

[0019] The modified polyethylene glycol diacrylate of the present invention introduces a dissociable anionic group through 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. After dissociation, the anionic group can move freely and migrate in the polymer network, providing a good ion migration channel and giving it a high ionic conductivity. It can migrate directionally with the cations in the polyurethane acrylate under the action of an electric field, generating electrostatic attraction / repulsion, and achieving the effect of reducing viscosity through electrolysis.

[0020] As a preferred embodiment of the present invention, the polyurethane acrylate is a cationic polyurethane acrylate; the preparation method of the cationic polyurethane acrylate includes: preparing intermediate A using acetone glycerol, p-toluenesulfonyl chloride and pyridine as raw materials; heating and stirring intermediate A and p-bromophenol to obtain intermediate B; reacting intermediate B and zinc nitrate hexahydrate at elevated temperature to obtain intermediate C; reacting intermediate C and 1,6-bis(diphenylphosphino)hexane with stirring to obtain a quaternary phosphonium salt; and preparing the cationic polyurethane acrylate using the quaternary phosphonium salt, isophorone diisocyanate, polyether polyol and 2-hydroxyethyl acrylate as raw materials.

[0021] The cationic polyurethane acrylate of the present invention is prepared from acetone glycerol, p-toluenesulfonyl chloride, pyridine, p-bromophenol, zinc nitrate hexahydrate and 1,6-bis(diphenylphosphino)hexane to obtain a quaternary phosphonium salt, which is then reacted with isophorone diisocyanate, polyether polyol, 2-hydroxyethyl acrylate and other raw materials to obtain the quaternary phosphonium salt cationic polyurethane acrylate.

[0022] As a preferred technical solution of the present invention, the preparation steps of intermediate A are as follows: by weight, 12-14 parts of acetone glycerol and 24-28 parts of p-toluenesulfonyl chloride are mixed, and then 24-26 parts of pyridine are added. The mixture is stirred at 0-4°C for 20-24 hours, distilled under reduced pressure, washed successively with deionized water and saturated sodium bicarbonate solution, and dried to obtain intermediate A.

[0023] As a preferred technical solution of the present invention, the preparation steps of intermediate B are as follows: by weight, 14-16 parts of intermediate A and 14-16 parts of p-bromophenol are added to 40-50 parts of N,N-dimethylformamide, heated and stirred at 80-90°C for 30-36 hours, the solvent is removed by rotary evaporation, washed with water, dried, and subjected to chromatography to obtain intermediate B.

[0024] Under heating conditions, p-bromophenol in N,N-dimethylformamide undergoes partial deprotonation to generate the nucleophile p-bromophenoxy anion. This anion attacks the carbon atom adjacent to the sulfonate in intermediate A, and the sulfonate is substituted as a leaving group to form a new C–O ether bond, thereby preparing intermediate B.

[0025] As a preferred technical solution of the present invention, the preparation steps of intermediate C are as follows: by weight, 6-8 parts of intermediate B are added to 24-30 parts of acetonitrile and stirred evenly, then 12-16 parts of zinc nitrate hexahydrate are added and reacted at 60-70°C for 10-12 hours, washed with water, dried, and subjected to chromatography to obtain intermediate C.

[0026] As a preferred technical solution of the present invention, the preparation steps of the quaternary phosphonium salt are as follows: by weight, 2-4 parts of intermediate C and 1-3 parts of 1,6-bis(diphenylphosphine)hexane are mixed, and then 4-6 parts of ethylene glycol and 0.4-0.8 parts of nickel bromide are added. The mixture is heated to 180-190°C under a nitrogen atmosphere and reacted for 20-24 hours. After the reaction is complete, the mixture is cooled, washed with water, and dried to obtain the quaternary phosphonium salt.

[0027] As a preferred technical solution of the present invention, the preparation steps of the cationic polyurethane acrylate are as follows: by weight, 0.2-0.4 parts of the quaternary phosphonium salt and 1-3 parts of isophorone diisocyanate are mixed, heated to 50-60°C and stirred for 60-80 min, then 0.04-0.06 parts of dibutyltin dilaurate and 8-10 parts of polyether polyol are added and stirred for 2-4 h, the temperature is controlled at 40-50°C, and then 0.4-0.6 parts of 2-hydroxyethyl acrylate are added and stirred for 2-4 h to obtain the cationic polyurethane acrylate.

[0028] The cationic polyurethane acrylate of this invention grafts quaternary phosphonium salt groups into the polyurethane acrylate segments to form positively charged quaternary phosphonium salt groups. The quaternary phosphonium salt cations and the dissociable anionic groups of the modified polyethylene glycol diacrylate form a dynamic cross-linking network through strong electrostatic attraction, giving the tape stable adhesion under normal conditions. When an electric field is applied, the system undergoes directional ion migration and cross-linking relaxation, and the adhesion is significantly reduced, thereby achieving the effect of reducing adhesion through electricity.

[0029] As a preferred embodiment of the present invention, the montmorillonite is a humic acid / montmorillonite composite; the preparation method of the humic acid / montmorillonite composite includes: adding 0.1-0.5 parts by weight of humic acid and 8-10 parts by weight of commercially available montmorillonite to 70-80 parts by weight of deionized water, shaking at 500-600 r / min for 60-80 h at 40-50°C, and freeze-drying to obtain the humic acid / montmorillonite composite.

[0030] This invention uses humic acid and montmorillonite as raw materials. Montmorillonite has a silicate lamellar stacked structure with certain gaps in the middle and a small number of fish scale-like fragments on the surface, which have good adsorption properties. Humic acid molecules contain carboxyl groups, hydroxyl groups and aromatic structures. The hydrogen bonding or π-π stacking between molecules causes humic acid to form polymers stacked on the surface of montmorillonite, thus forming a humic acid / montmorillonite composite with montmorillonite as the skeleton and humic acid loaded on the surface.

[0031] As a preferred embodiment of the present invention, the plasticizer is diisobutyl phthalate.

[0032] As a preferred embodiment of the present invention, the antioxidant is butylated hydroxytoluene or benzotriazole.

[0033] A second aspect of the present invention provides an anti-plasticizer precipitation, electrically conductive, non-sticky adhesive tape prepared by the preparation method described in the first aspect.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) In this invention, a modified polyethylene glycol diacrylate is prepared by using polyethylene glycol diacrylate and 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as raw materials. The modified polyethylene glycol diacrylate is then combined with cationic polyurethane acrylate, humic acid / montmorillonite complex, 2-hydroxy-2-methylphenylacetone, plasticizer and oxidant to prepare an electrostatically conductive and non-sticky tape. The plasticizer diisobutyl phthalate is adsorbed by the humic acid / montmorillonite complex to avoid precipitation. At the same time, the cationic polyurethane acrylate grafts quaternary phosphonium salt groups into the polyurethane acrylate chain to form positively charged quaternary phosphonium salt groups. The quaternary phosphonium salt cations interact with the dissociable anionic groups of the modified polyethylene glycol diacrylate to achieve electrostatically conductive and non-sticky tape, and effectively avoids the appearance of residual adhesive after electrostatic application.

[0036] (2) In the humic acid / montmorillonite composite of the present invention, montmorillonite has nanoscale interlayer spacing and huge specific surface area. Its interlayer can adsorb plasticizer diisobutyl phthalate through van der Waals forces and electrostatic interactions. In addition, humic acid contains a large number of non-polar aromatic rings and alkane chains, which can interact strongly with diisobutyl phthalate, thereby achieving adsorption of it, avoiding the precipitation of plasticizer, and effectively avoiding residual glue after electrolysis. Attached Figure Description

[0037] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0038] Figure 1 This is a schematic diagram illustrating the preparation of quaternary phosphonium salt in Example 1 of the present invention.

[0039] Figure 2 The infrared spectra of the humic acid / montmorillonite complex and montmorillonite in Example 1 of this invention are shown. Detailed Implementation

[0040] To facilitate understanding of the present invention, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of the invention.

[0041] The sources of some components in the examples and comparative examples are as follows:

[0042] Commercially available polyethylene glycol diacrylate, product number P131592, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0043] 1-Allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, product number A304296, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0044] Acetone glycerol, CAS No. 100-79-8, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0045] p-Toluenesulfonyl chloride, CAS No. 98-59-9, was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0046] p-Bromophenol, CAS No. 106-41-2, was purchased from Sinopharm Chemical Reagent Co., Ltd.

[0047] Zinc nitrate hexahydrate, CAS No. 10196-18-6, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0048] 1,6-Bis(diphenylphosphino)hexane, CAS No. 19845-69-3, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0049] Nickel bromide, CAS No. 13462-88-9, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0050] Isophorone diisocyanate, product number I109582, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0051] Polyether polyol, item number JS0546, purchased from Hubei Jusheng Technology Co., Ltd.

[0052] 2-Hydroxyethyl acrylate, CAS No. 818-61-1, purchased from Shanghai Huayuan Biochemical Technology Co., Ltd.

[0053] Commercially available polyurethane acrylate, product number js2024121015, was purchased from Wuhan Jushun Chemical Co., Ltd.

[0054] Commercially available montmorillonite, product number M141491, was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0055] Humic acid, CAS No. 1415-93-6, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0056] 2-Hydroxy-2-methylphenylacetone, CAS No. 7473-98-5, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0057] Diisobutyl phthalate, product number M27794, was purchased from Shanghai Mairui Biochemical Technology Co., Ltd.

[0058] Butylated hydroxytoluene, CAS No. 50356-19-9, was purchased from Wuhan Jiyesheng Chemical Co., Ltd.

[0059] Benzotriazole, CAS No. 95-14-7, was purchased from Shanghai Maclean Biochemical Technology Co., Ltd.

[0060] Example 1:

[0061] This embodiment provides a method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape, comprising the following steps:

[0062] S1. By weight, 40 parts of modified polyethylene glycol diacrylate, 40 parts of cationic polyurethane acrylate, 8 parts of humic acid / montmorillonite complex, 4 parts of 2-hydroxy-2-methylphenylacetone, 3 parts of plasticizer diisobutyl phthalate and 3 parts of antioxidant dibutylhydroxytoluene are stirred and mixed to obtain a mixture.

[0063] S2. The mixture is coated onto a release film using a doctor blade coater and UV cured for 80 seconds to obtain an adhesive layer. Then, a protective film is attached to the adhesive layer to obtain an anti-plasticizer exudation, electrically conductive, non-sticky tape.

[0064] Preparation of the modified polyethylene glycol diacrylate: 3 parts by weight of 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 20 parts by weight of commercially available polyethylene glycol diacrylate and 0.5 parts by weight of azobisisobutyronitrile were added to 120 parts by weight of anhydrous ethanol and stirred. The mixture was then polymerized at 60°C for 10 hours under a nitrogen atmosphere and dried under vacuum to obtain the modified polyethylene glycol diacrylate.

[0065] Preparation of cationic polyurethane acrylate: 14 parts by weight of acetone glycerol and 28 parts by weight of p-toluenesulfonyl chloride were mixed, then 26 parts by weight of pyridine were added and stirred at 4°C for 20 h. The mixture was then distilled under reduced pressure, washed successively with deionized water and saturated sodium bicarbonate solution, and dried to obtain intermediate A. 16 parts by weight of intermediate A and 16 parts by weight of p-bromophenol were added to 50 parts by weight of N,N-dimethylformamide, and heated and stirred at 90°C for 30 h. The solvent was removed by rotary evaporation, washed with water, dried, and subjected to chromatography to obtain intermediate B. 8 parts by weight of intermediate B were added to 30 parts by weight of acetonitrile and stirred until homogeneous. Then, 16 parts by weight of zinc nitrate hexahydrate were added and reacted at 70°C for 10 h. The mixture was washed with water, dried, and subjected to chromatography to obtain intermediate C. Four parts of intermediate C were mixed with three parts of 1,6-bis(diphenylphosphine)hexane, and then six parts of ethylene glycol and 0.8 parts of nickel bromide were added. The mixture was heated to 190°C under a nitrogen atmosphere and reacted for 20 hours. After the reaction was complete, the mixture was cooled, washed with water, and dried to obtain a quaternary phosphonium salt. 0.4 parts of the quaternary phosphonium salt and three parts of isophorone diisocyanate were mixed, heated to 60°C, and stirred for 60 minutes. Then, 0.06 parts of dibutyltin dilaurate and 10 parts of polyether polyol were added, and the mixture was stirred for another 2 hours while maintaining the temperature at 50°C. Finally, 0.6 parts of 2-hydroxyethyl acrylate were added, and the mixture was stirred for another 2 hours to obtain cationic polyurethane acrylate.

[0066] Preparation of humic acid / montmorillonite complex: 0.5 parts by weight of humic acid and 10 parts by weight of commercially available montmorillonite were added to 80 parts by weight of deionized water, shaken at 600 r / min for 60 h at 50 °C, and then freeze-dried to obtain humic acid / montmorillonite complex.

[0067] Example 2:

[0068] This embodiment provides a method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape, comprising the following steps:

[0069] S1. By weight, 30 parts of modified polyethylene glycol diacrylate, 30 parts of cationic polyurethane acrylate, 4 parts of humic acid / montmorillonite complex, 2 parts of 2-hydroxy-2-methylphenylacetone, 1 part of plasticizer diisobutyl phthalate and 1 part of antioxidant benzotriazole are stirred and mixed to obtain a mixture.

[0070] S2. The mixture is coated onto a release film using a doctor blade coater and UV cured for 60 seconds to obtain an adhesive layer. Then, a protective film is attached to the adhesive layer to obtain an anti-plasticizer exudation, electrically conductive, non-sticky tape.

[0071] Preparation of the modified polyethylene glycol diacrylate: 1 part by weight of 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 10 parts by weight of commercially available polyethylene glycol diacrylate and 0.3 parts by weight of azobisisobutyronitrile were added to 100 parts by weight of anhydrous ethanol and stirred. The mixture was then polymerized at 50°C for 12 hours under a nitrogen atmosphere and dried under vacuum to obtain the modified polyethylene glycol diacrylate.

[0072] Preparation of cationic polyurethane acrylate: By weight, 12 parts of acetone glycerol and 24 parts of p-toluenesulfonyl chloride were mixed, then 24 parts of pyridine were added and stirred at 0℃ for 24 h. The mixture was then distilled under reduced pressure, washed successively with deionized water and saturated sodium bicarbonate solution, and dried to obtain intermediate A. 14 parts of intermediate A and 14 parts of p-bromophenol were added to 40 parts of N,N-dimethylformamide, and heated and stirred at 80℃ for 36 h. The solvent was removed by rotary evaporation, washed with water, dried, and subjected to chromatography to obtain intermediate B. 6 parts of intermediate B were added to 24 parts of acetonitrile and stirred until homogeneous. Then, 12 parts of zinc nitrate hexahydrate were added and reacted at 60℃ for 12 hours. h, wash with water, dry, and chromatographically to obtain intermediate C; mix 2 parts of intermediate C with 1 part of 1,6-bis(diphenylphosphine)hexane, then add 4 parts of ethylene glycol and 0.4 parts of nickel bromide, heat to 180℃ under nitrogen atmosphere and react for 24 h, after the reaction is complete, cool, wash with water, and dry to obtain quaternary phosphonium salt; mix 0.2 parts of the quaternary phosphonium salt and 1 part of isophorone diisocyanate, heat to 50℃ and stir for 80 min, then add 0.04 parts of dibutyltin dilaurate and 8 parts of polyether polyol and continue stirring for 4 h, controlling the temperature at 40℃, then add 0.4 parts of 2-hydroxyethyl acrylate and stir for 4 h to obtain cationic polyurethane acrylate.

[0073] Preparation of humic acid / montmorillonite complex: 0.1 parts by weight of humic acid and 8 parts by weight of commercially available montmorillonite were added to 70 parts by weight of deionized water, shaken at 500 r / min for 80 h at 40 °C, and then freeze-dried to obtain humic acid / montmorillonite complex.

[0074] Example 3:

[0075] This embodiment provides a method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape, comprising the following steps:

[0076] S1. By weight, 35 parts of modified polyethylene glycol diacrylate, 35 parts of cationic polyurethane acrylate, 6 parts of humic acid / montmorillonite complex, 3 parts of 2-hydroxy-2-methylphenylacetone, 2 parts of plasticizer diisobutyl phthalate and 2 parts of antioxidant dibutylhydroxytoluene are stirred and mixed to obtain a mixture.

[0077] S2. The mixture is coated onto a release film using a doctor blade coater and UV cured for 70 seconds to obtain an adhesive layer. Then, a protective film is attached to the adhesive layer to obtain an anti-plasticizer exudation, electrically conductive, non-sticky tape.

[0078] Preparation of the modified polyethylene glycol diacrylate: By weight, 2 parts of 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 15 parts of commercially available polyethylene glycol diacrylate and 0.4 parts of azobisisobutyronitrile were added to 110 parts of anhydrous ethanol and stirred and mixed. The mixture was then polymerized at 55°C for 11 hours under a nitrogen atmosphere and dried under vacuum to obtain the modified polyethylene glycol diacrylate.

[0079] Preparation of cationic polyurethane acrylate: By weight, 13 parts of acetone glycerol and 26 parts of p-toluenesulfonyl chloride were mixed, then 25 parts of pyridine were added and stirred at 2℃ for 22 h. The mixture was then distilled under reduced pressure, washed successively with deionized water and saturated sodium bicarbonate solution, and dried to obtain intermediate A. 15 parts of intermediate A and 15 parts of p-bromophenol were added to 45 parts of N,N-dimethylformamide, and heated and stirred at 85℃ for 33 h. The solvent was removed by rotary evaporation, washed with water, dried, and subjected to chromatography to obtain intermediate B. 7 parts of intermediate B were added to 26 parts of acetonitrile and stirred until homogeneous. Then, 14 parts of zinc nitrate hexahydrate were added and reacted at 65℃ for 11 hours. h, wash with water, dry, and chromatographically to obtain intermediate C; mix 3 parts of intermediate C with 2 parts of 1,6-bis(diphenylphosphine)hexane, then add 5 parts of ethylene glycol and 0.6 parts of nickel bromide, heat to 185℃ under nitrogen atmosphere and react for 22h. After the reaction is complete, cool, wash with water, and dry to obtain quaternary phosphonium salt; mix 0.3 parts of the quaternary phosphonium salt with 2 parts of isophorone diisocyanate, heat to 55℃ and stir for 70min, then add 0.05 parts of dibutyltin dilaurate and 9 parts of polyether polyol and continue stirring for 3h, controlling the temperature at 45℃, then add 0.5 parts of 2-hydroxyethyl acrylate and stir for 3h to obtain cationic polyurethane acrylate.

[0080] Preparation of humic acid / montmorillonite complex: 0.3 parts by weight of humic acid and 9 parts by weight of commercially available montmorillonite were added to 75 parts by weight of deionized water, shaken at 550 r / min for 70 h at 45 °C, and then freeze-dried to obtain humic acid / montmorillonite complex.

[0081] Comparative Example 1

[0082] The difference between this comparative example and Example 1 is that commercially available polyethylene glycol diacrylate (product number P131592) was used instead of modified polyethylene glycol diacrylate.

[0083] Comparative Example 2

[0084] The difference between this comparative example and Example 1 is that commercially available polyurethane acrylate (product number js2024121015) was used instead of cationic polyurethane acrylate.

[0085] Comparative Example 3

[0086] The difference between this comparative example and Example 1 is that commercially available montmorillonite (product number M141491) was used instead of the humic acid / montmorillonite complex.

[0087] Remove the protective film from the electrically conductive anti-adhesive tape of the above embodiments and comparative examples, attach it to the steel plate, and place it at 23°C for 24 hours before conducting performance testing. The test method is as follows:

[0088] Shear strength test: The test shall be conducted in accordance with the requirements of GB / T 7124-2008 Determination of tensile shear strength of adhesives.

[0089] Peel strength test before power application: The test shall be conducted in accordance with the requirements of GB / T 2792-2014 Test method for peel strength of adhesive tape.

[0090] Peel strength test after energization: The energized anti-adhesion tape on the steel plate is energized at 10V for 30s, the peel strength of the tape after energization is tested, and whether there is any residual adhesive on the surface is observed.

[0091] The performance test data above are shown in Table 1.

[0092]

[0093] As can be seen from the above, the present invention uses polyethylene glycol diacrylate and 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as raw materials to prepare modified polyethylene glycol diacrylate, and combines it with cationic polyurethane acrylate, humic acid / montmorillonite complex, 2-hydroxy-2-methylphenylacetone, plasticizer and oxidant to prepare an electrically conductive and non-adhesive tape. The humic acid / montmorillonite complex adsorbs the plasticizer diisobutyl phthalate to prevent precipitation, and the dissociable anionic groups and cationic groups achieve non-adhesive bonding through electrolysis, effectively avoiding the appearance of residual adhesive after electrolysis (Examples 1 to 3).

[0094] Compared to Example 1, using commercially available polyethylene glycol diacrylate (product number P131592) instead of modified polyethylene glycol diacrylate resulted in a lack of dissociable anionic groups in the tape, leading to poor tack reduction effect upon electrolysis and the appearance of residue after electrolysis (Comparative Example 1); compared to Example 1, using commercially available polyurethane acrylate (product number js2024121015) instead of cationic polyurethane acrylate resulted in a lack of positively charged quaternary phosphonium salt groups in the tape, leading to poor tack reduction effect upon electrolysis and the appearance of residue after electrolysis (Comparative Example 2); compared to Example 1, using commercially available montmorillonite (product number M141491) instead of humic acid / montmorillonite composite resulted in poorer adsorption of plasticizers, leading to residue after electrolysis (Comparative Example 3).

Claims

1. A method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape, characterized in that, Includes the following steps: S1. By weight, 30-40 parts of modified polyethylene glycol diacrylate, 30-40 parts of cationic polyurethane acrylate, 4-8 parts of humic acid / montmorillonite complex, 2-4 parts of 2-hydroxy-2-methylphenylacetone, 1-3 parts of plasticizer and 1-3 parts of antioxidant are stirred and mixed to obtain a mixture. S2. The mixture is coated onto a release film using a doctor blade coater and UV cured for 60-80 seconds to obtain an adhesive layer. Then, a protective film is attached to the adhesive layer to obtain an anti-plasticizer exudation, electrically conductive, non-sticky tape. The method for preparing the modified polyethylene glycol diacrylate includes: using polyethylene glycol diacrylate and 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide as raw materials, a polymerization reaction is carried out under the action of azobisisobutyronitrile to obtain the modified polyethylene glycol diacrylate. The preparation method of the cationic polyurethane acrylate includes: preparing intermediate A using acetone glycerol, p-toluenesulfonyl chloride and pyridine as raw materials; heating and stirring intermediate A and p-bromophenol to obtain intermediate B; reacting intermediate B and zinc nitrate hexahydrate at elevated temperature to obtain intermediate C; reacting intermediate C and 1,6-bis(diphenylphosphino)hexane with stirring to obtain a quaternary phosphonium salt; and preparing the cationic polyurethane acrylate using the quaternary phosphonium salt, isophorone diisocyanate, polyether polyol and 2-hydroxyethyl acrylate as raw materials. The preparation method of the humic acid / montmorillonite composite includes: adding 0.1-0.5 parts by weight of humic acid and 8-10 parts by weight of commercially available montmorillonite to 70-80 parts by weight of deionized water, shaking at 500-600 r / min for 60-80 h at 40-50℃, and freeze-drying to obtain the humic acid / montmorillonite composite.

2. The method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape according to claim 1, characterized in that, The polymerization reaction steps are as follows: by weight, 1-3 parts of 1-allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide, 10-20 parts of commercially available polyethylene glycol diacrylate and 0.3-0.5 parts of azobisisobutyronitrile are added to 100-120 parts of anhydrous ethanol and stirred and mixed. The mixture is then placed under a nitrogen atmosphere and polymerized at 50-60°C for 10-12 hours, followed by vacuum drying.

3. The method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape according to claim 1, characterized in that, The preparation steps of intermediate A are as follows: by weight, 12-14 parts of acetone glycerol and 24-28 parts of p-toluenesulfonyl chloride are mixed, and then 24-26 parts of pyridine are added. The mixture is stirred at 0-4℃ for 20-24 hours, distilled under reduced pressure, washed successively with deionized water and saturated sodium bicarbonate solution, and dried to obtain intermediate A.

4. The method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape according to claim 1, characterized in that, The preparation steps of intermediate B are as follows: by weight, 14-16 parts of intermediate A and 14-16 parts of p-bromophenol are added to 40-50 parts of N,N-dimethylformamide, heated and stirred at 80-90°C for 30-36 hours, the solvent is removed by rotary evaporation, washed with water, dried, and subjected to chromatography to obtain intermediate B.

5. The method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape according to claim 1, characterized in that, The preparation steps of intermediate C are as follows: by weight, 6-8 parts of intermediate B are added to 24-30 parts of acetonitrile and stirred evenly, then 12-16 parts of zinc nitrate hexahydrate are added and reacted at 60-70℃ for 10-12 hours, washed with water, dried, and subjected to chromatography to obtain intermediate C.

6. The method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape according to claim 1, characterized in that, The preparation steps of the quaternary phosphonium salt are as follows: by weight, 2-4 parts of intermediate C and 1-3 parts of 1,6-bis(diphenylphosphine)hexane are mixed, and then 4-6 parts of ethylene glycol and 0.4-0.8 parts of nickel bromide are added. The mixture is heated to 180-190℃ under a nitrogen atmosphere and reacted for 20-24 hours. After the reaction is complete, the mixture is cooled, washed with water, and dried to obtain the quaternary phosphonium salt.

7. The method for preparing an anti-plasticizer exudation, electrically conductive, non-sticky adhesive tape according to claim 1, characterized in that, The preparation steps of the cationic polyurethane acrylate are as follows: by weight, 0.2-0.4 parts of the quaternary phosphonium salt and 1-3 parts of isophorone diisocyanate are mixed, heated to 50-60℃ and stirred for 60-80 min, then 0.04-0.06 parts of dibutyltin dilaurate and 8-10 parts of polyether polyol are added and stirred for 2-4 h, the temperature is controlled at 40-50℃, and then 0.4-0.6 parts of 2-hydroxyethyl acrylate are added and stirred for 2-4 h to obtain the cationic polyurethane acrylate.

8. A current-conducting, non-sticky adhesive tape that resists plasticizer exudation, characterized in that, It is prepared by the preparation method according to any one of claims 1 to 7.

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