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CN-122010789-A - Preparation method of recyclable eutectic solvent adhesive with wide temperature range

CN122010789ACN 122010789 ACN122010789 ACN 122010789ACN-122010789-A

Abstract

The invention relates to a preparation method of a recyclable eutectic solvent adhesive with a wide temperature range, which comprises the steps of firstly synthesizing bola type amine oxides with different carbon chain lengths, taking the bola type amine oxides as hydrogen bond acceptors, taking citric acid as hydrogen bond donors, and successfully preparing the recyclable eutectic solvent adhesive with the wide temperature range. The eutectic solvent adhesive prepared by the invention has excellent comprehensive performance in engineering application. Aiming at various substrates such as glass, metal, plastic and the like, the material shows more excellent bonding capability, and effectively solves the problem of uneven adhesive force among different materials of the traditional adhesive. Ensures that the glued product has stable structure, can maintain visual beautiful degree, and perfectly meets the requirements of modern precision manufacturing on the appearance of the finished product.

Inventors

  • FENG LEI
  • FU WENWEN
  • LI HONGGUANG

Assignees

  • 山东大学

Dates

Publication Date
20260512
Application Date
20260130

Claims (10)

  1. 1. A method for preparing a hydrogen bond acceptor, comprising the steps of: (1) Mixing tertiary amine and ethanol, stirring, heating and raising the temperature to obtain a mixture a; (2) Slowly dripping hydrogen peroxide into the mixture a, preserving heat, and stopping the reaction to obtain a mixture b; (3) Concentrating the mixture b by vacuum rotary evaporation, adding an organic solvent, and recrystallizing to obtain white bola-type amine oxide with different carbon chain lengths, namely a hydrogen bond acceptor.
  2. 2. The process according to claim 1, wherein in the step (1), the tertiary amine is N, N, N ', N' -tetramethyl ethylenediamine, N, N, N ', N' -tetramethyl butanediamine or N, N, N ', N' -tetramethyl hexanediamine, the volume ratio of the molar amount of the tertiary amine to ethanol is (1-50): (10-300), the unit mmol/mL, and the heating temperature is 30-80 ℃.
  3. 3. The process according to claim 1, wherein in the step (2), the molar ratio of hydrogen peroxide to tertiary amine added is (10-60): 1-50, and the incubation time is 6-24 hours.
  4. 4. The preparation method of claim 1, wherein in the step (3), the organic solvent selected for recrystallization is a mixed solution of ethyl acetate and petroleum ether, and the volume ratio of the two is 5:1-1:5.
  5. 5. The preparation method of the recyclable eutectic solvent adhesive with a wide temperature range comprises the following steps: mixing the hydrogen bond acceptor prepared in claim 1 with a hydrogen bond donor, adding water for dissolution, and removing water in the mixture to obtain the eutectic solvent adhesive.
  6. 6. The method of claim 5, wherein the hydrogen bond donor is an organic carboxylic acid and the organic carboxylic acid is citric acid.
  7. 7. The method according to claim 5, wherein the molar ratio of hydrogen bond donor to hydrogen bond acceptor is 2:1-1:3, and the water removal is performed by natural evaporation, rotary evaporation and freeze-drying.
  8. 8. A broad temperature range recyclable eutectic solvent adhesive prepared by the method of claim 5.
  9. 9. The broad temperature range recyclable eutectic solvent adhesive according to claim 8, wherein the loaded substrate is glass, iron, plastic, and is directly smeared on a substrate, the application temperature range is wide, the adhesive has strong adhesion capability in the range of-50 ℃ to 50 ℃, the adhesive still shows excellent performance at low temperature, the adhesive strength reaches 140 MPa at-50 ℃, and the adhesive can exist in a static solvent in a short time and has strong adhesion.
  10. 10. The broad temperature range recyclable eutectic solvent adhesive of claim 8, wherein the eutectic solvent adhesive has strong adhesion after being placed for one year, can be used for a long time even without isolating air, is simple to debond without leaving any trace, can be debonded by repeated washing with flowing water, has substantially unchanged adhesion after multiple recycling cycles, and has flexibility and fluidity at low temperature.

Description

Preparation method of recyclable eutectic solvent adhesive with wide temperature range Technical Field The invention relates to a preparation method of a recyclable eutectic solvent adhesive with a wide temperature range, belonging to the technical field of supermolecule adhesives. Background The advent and use of adhesives has played an irreplaceable role throughout human history. In ancient times, people collected natural raw materials from animals and plants to prepare adhesives. With the development of the chemical industry, particularly the petrochemical industry, binary polymerizable adhesives have been vigorously developed. The bonding process of polymeric adhesives often involves covalent bond formation, physical entanglement and supramolecular interactions, enabling strong adhesion to common substrates, and has many advantages over natural adhesives, single component adhesives, including high bond strength, good long term stability, lower cost, etc. Polymeric adhesives, however, also suffer from a number of problems such as being difficult to remove after bonding, not recyclable, and being difficult to avoid using hazardous solvents (including benzene, toluene, xylenes, formaldehyde and other volatile organic compounds) during the manufacturing process. In order to overcome the above drawbacks, in recent years, there has been a strong demand for a supermolecule adhesive having recyclable properties, particularly a low-toxicity/non-toxic adhesive. Eutectic solvents are supramolecular assembly systems composed of hydrogen bond donors and acceptors via hydrogen bonds, capable of forming viscous liquids in the absence of solvents. These properties make it very suitable for use as a supramolecular adhesive. However, most eutectic solvent adhesives have glass transition temperatures above 0 ℃ and are difficult to use in low temperature environments, limiting their range of application. In order to overcome the above drawbacks, the market has recently been pressing for supramolecular adhesives with recyclable properties, in particular low-toxic/non-toxic adhesives. Eutectic solvents are supermolecular systems formed by the assembly of hydrogen bond donors and hydrogen bond acceptors by hydrogen bonding, which can form viscous liquids in the absence of solvents. These properties make it very suitable for use as a raw material for the preparation of supramolecular adhesives or directly as a supramolecular adhesive. However, most eutectic solvent-based adhesives have a glass transition temperature of 0 ℃ or higher, are difficult to apply in a low-temperature environment, and have a narrow use temperature range, thereby limiting the application range. Disclosure of Invention Aiming at the defects existing in the prior art, the invention provides a preparation method of a recyclable eutectic solvent adhesive with a wide temperature range. The method has the advantages of simple process, high atom utilization rate, low price of the adopted hydrogen bond donor, easy acquisition, convenient large-scale preparation, strong adhesion of the prepared adhesive, wide application temperature range, strong adhesion capability within the range of-50 ℃ to 50 ℃, excellent performance at low temperature, and high adhesive strength of 140MPa at-50 ℃, and is obviously superior to the similar adhesive. The technical scheme of the invention is as follows: it is a first object of the present invention to provide a method for preparing hydrogen bond acceptors. A method for preparing a hydrogen bond acceptor, comprising the steps of: (1) Mixing tertiary amine and ethanol, stirring, heating and raising the temperature to obtain a mixture a; (2) Slowly dripping hydrogen peroxide into the mixture a, preserving heat, and stopping the reaction to obtain a mixture b; (3) Concentrating the mixture b by vacuum rotary evaporation, adding an organic solvent, and recrystallizing to obtain white bola-type amine oxide with different carbon chain lengths, namely a hydrogen bond acceptor. According to a preferred embodiment of the present invention, in step (1), the tertiary amine is N, N, N ', N' -tetramethyl ethylenediamine, N, N, N ', N' -tetramethyl butanediamine or N, N, N ', N' -tetramethyl hexamethylenediamine. According to the invention, in step (1), the molar amount of tertiary amine to the volume ratio of ethanol is preferably (1-50): (10-300), in mmol/mL. According to a preferred embodiment of the invention, in step (1), the heating temperature is 30-80 ℃. According to the invention, preferably, in step (2), hydrogen peroxide is added in a molar ratio of (10-60) to (1-50) to the tertiary amine. According to the invention, in step (2), the incubation time is preferably from 6 to 24 hours. According to the invention, in the step (3), the organic solvent selected for recrystallization is a mixed solution of ethyl acetate and petroleum ether, and the volume ratio of the ethyl acetate to the petroleum ether is 5:1-1:5. The second object of