CN113621340A - Photo-reversible adhesive containing anthracene group and preparation method and application thereof - Google Patents

Photo-reversible adhesive containing anthracene group and preparation method and application thereof Download PDF

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CN113621340A
CN113621340A CN202010376416.9A CN202010376416A CN113621340A CN 113621340 A CN113621340 A CN 113621340A CN 202010376416 A CN202010376416 A CN 202010376416A CN 113621340 A CN113621340 A CN 113621340A
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anthracene
gas
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allyl
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CN113621340B (en
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程珏
沈丽娇
张军营
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J181/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur, with or without nitrogen, oxygen, or carbon only; Adhesives based on polysulfones; Adhesives based on derivatives of such polymers
    • C09J181/02—Polythioethers; Polythioether-ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds

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  • Adhesives Or Adhesive Processes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a light reversible adhesive containing anthracene group, which introduces anthracene group in the structure, so that the adhesive has excellent light reversible bonding performance. Firstly, raw materials containing anthracene-based compounds are allylated to prepare allylated products containing anthracene, and then the allylated products are mixed with mercaptan and a photosensitizer and react under ultraviolet light to prepare the light reversible adhesive containing anthracene-based groups. According to the invention, the anthracene ring is successfully introduced into the adhesive, so that the adhesive is cured under 350-370 nm ultraviolet light and degraded under 220-280 nm ultraviolet light, and photo-reversible bonding is realized, and the synthesis method is simple and convenient, high in yield and high in purity; the raw materials are easy to obtain, only the photoreaction is used, and the process is green and environment-friendly.

Description

Photo-reversible adhesive containing anthracene group and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adhesives, and particularly relates to a photo-reversible adhesive containing anthracene-based groups, and a preparation method and application thereof.
Background
The adhesive is a substance with excellent adhesive property, and is widely used in various fields of national economy. They are essential materials for the automotive, biomedical, architectural and aerospace industries. Conventional structural adhesives are difficult to separate from the bonding interface. With the development of modern scientific technology, reworkable adhesives with reusable adhesion are expected for material recycling.
Currently, detachable adhesives are mainly based on a thermoreversible mechanism, and light-induced reworkable adhesives have been receiving attention because of their rapid and simple operation. Recently, it has been reported that an azobenzene-Based photoisomerizable adhesive (Shotaro Ito; Haruhisa Akiyama. light-Induced Reworkable Adhesives Based on ABA-type Triblock copolymer with azo polymer Terminami. ACS appl. Mater. Interfaces2018,10,32649-32658) can be adjusted in its adhesive strength by light due to trans-cis isomerization of azobenzene. However, the azobenzene-based photosensitive reworkable adhesives have unsatisfactory mechanical properties, with the bond strength changing from 1.5 to 2.0MPa for trans-isomerization to 0.5 to 0.1MPa for cis-isomerization.
Recently, a reversible underwater adhesive (Wang, Z.; Guo, L.; Xiao, H.; Cong, H.; Wang, S.A reversible underswater glue base on photo-and thermo-reactive chemical bonds. Mater. horiz.2020,7, 282-.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a light reversible adhesive containing anthracene group, which is a light-sensitive reworkable adhesive with excellent adhesive property. Firstly, allylating an anthracene-based compound raw material to prepare an anthracene-based allylated product, mixing the anthracene-based allylated product with a thiol compound and a photosensitizer, and carrying out [4+4] cycloaddition reaction and Click reaction under ultraviolet light to prepare the anthracene-based group-containing reversible adhesive.
One of the objects of the present invention is to provide a photo-reversible adhesive containing an anthracene group, which contains the following structure:
Figure BDA0002480244220000021
wherein R is1And R3ArbitrarySelected from alkyl, alkoxy or alkyl ester group with 1-20 carbon atoms, R2Is an alkoxy group or an alkyl ester group having 1 to 3 carbon atoms.
The second object of the present invention is to provide a method for preparing the above-mentioned photo-reversible adhesive containing an anthracene group, comprising the steps of: firstly, reacting an anthracene-based compound with an allyl compound to obtain an allyl product containing anthracene groups, then adding a thiol compound and a photosensitizer, and irradiating by ultraviolet light to obtain the light reversible adhesive containing anthracene groups. The method specifically comprises the following steps:
step one, dissolving an anthracene-based compound in a solvent, then adding anhydrous potassium carbonate, dropwise adding an allyl compound while stirring, and stirring for reaction to obtain an allylation product containing anthracene groups;
and step two, adding the allylation product containing the anthracene group obtained in the step one into a thiol compound and a photosensitizer, uniformly stirring, and then carrying out a light irradiation reaction under ultraviolet light to obtain the light reversible adhesive containing the anthracene group.
In the first step, the anthracene-based compound is at least one selected from anthracene-based carboxylic acid compounds and anthracene-based alcohol compounds, preferably at least one selected from 9-anthracene carboxylic acid, 9-anthracene acetic acid, 9-anthracene methanol and 1- (9-anthracene-based) ethanol; the allyl compound is selected from at least one of allyl alcohol, allyl carboxylic acid and allyl halide, preferably selected from allyl halide, and more preferably selected from allyl bromide;
in the first step, the molar ratio of the anthracene-based compound to the anhydrous potassium carbonate to the allyl compound is 1:1: 1-1: 1.3: 1.3;
in the first step, the adopted solvent is a polar solvent and is at least one selected from tetrahydrofuran and N, N-dimethylformamide; the mass ratio of the anthracene-based compound to the solvent is 1: 5-1: 20;
the stirring reaction temperature in the first step is 0-30 ℃, and the stirring reaction time is 24-48 h.
In the second step, the molecular formula of the thiol compound is R- (SH)xWherein R is selected from alkyl, alkoxy or alkyl ester group with 1-20 carbon atoms, and x is 2 or 3; the thiol compound is selected from dithiol compoundsAnd a trithiol compound, wherein the dithiol compound is at least one selected from 2, 2' - (1, 2-ethanediylbenzoxy) bisethanethiol, ethanedithiol, propanedithiol, 2, 3-butanedithiol, hexanedithiol, decanedithiol and s-triazine dithiol, and the trithiol compound is at least one selected from trimethylolpropane tris (3-mercaptopropionate), propane-1, 2, 3-trithiol and 1,3, 5-triazine-2, 4, 6-trithiol. The molar ratio of the dithiol compound to the trithiol compound in the thiol compound is 1.5:1 to 15: 1.
In the second step, the molar ratio of the allyl product containing the anthracene group to the sulfydryl in the thiol compound is 1: 0.8-1: 1.2;
the photosensitizer in the second step is selected from at least one of benzil compounds, alkyl benzophenone compounds and benzophenone compounds, preferably at least one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and benzophenone; the amount of the photosensitizer is 0.5-2% of the total weight of the allylation product containing the anthracene group and the thiol compound by mass percentage;
in the second step, the wavelength of ultraviolet light is 350-370 nm; the illumination time of the ultraviolet light is 5-15 min.
In the preparation process of the photo-reversible adhesive, anhydrous potassium carbonate is added in the first step, and then the mixture is stirred in an ice water bath until the allyl compound is completely dripped, wherein the dripping speed of the allyl compound is 10-30 drops/min; and (3) centrifuging, extracting, rotary evaporating and drying the allyl product containing the anthracene group obtained in the step one, wherein the solvent used for extracting is at least one selected from toluene, chloroform and carboxylic ester. The centrifugation, extraction, rotary evaporation and drying operations can be performed in any conventional equipment capable of performing the operations.
The photo-reversible adhesive containing anthracene group or the photo-reversible adhesive prepared by the preparation method provided by the invention realizes reversible structure conversion of crosslinking-decrosslinking under the action of ultraviolet light. The photo-reversible adhesive can be crosslinked when the wavelength of ultraviolet light is 350-370 nm, and can be crosslinked when the wavelength of ultraviolet light is 220-280 nm. The photo-reversible adhesive provided by the invention has strong adhesive capacity due to the fact that [4+4] cycloaddition reaction and Click reaction occur under 350-370 nm ultraviolet light; under 220-280 nm ultraviolet light, a cyclobutane structure formed by anthracenyl cycloaddition is opened, a network is subjected to decrosslinking, and the bonding strength is reduced; and (3) exposing the substrate to ultraviolet light of 350-370 nm again, performing cycloaddition reaction on the anthracene group again, crosslinking the network again, and recovering the bonding strength.
According to the invention, the anthracene ring is successfully introduced into the adhesive, so that the adhesive can be cured under 350-370 nm ultraviolet light and degraded under 220-280 nm ultraviolet light, and photo-reversible bonding is realized. The photo-reversible adhesive containing the anthracene group provided by the invention has excellent bonding performance, the tensile shear strength can reach 3.4MPa, the strength after photo-degradation only remains 20% of the original strength, and the strength recovery rate of re-crosslinking can reach about 80%.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the anthracene group is introduced into the thiol-ene network, and the obtained adhesive has good reversible reaction capability due to the strong reversible reaction capability of the anthracene group, so that reversible bonding of the adhesive can be realized under ultraviolet irradiation, and the adhesive has beneficial bonding strength, has rapid and effective debonding and re-bonding capabilities, can well realize the repeated reuse of materials, and has a wide application prospect;
2. the preparation method provided by the invention has the advantages of simple and convenient synthesis method, high yield and high purity; and the raw materials are easy to obtain, the reaction can be completed only by using ultraviolet light, and the reaction process is green and environment-friendly.
Drawings
FIG. 1 is an infrared spectrum of 9-anthracenecarboxylic acid and allyl 9-anthracenecarboxylate in example 1, wherein curve 1a is an infrared spectrum of 9-anthracenecarboxylic Acid (AC) and curve 1b is an infrared spectrum of allyl 9-anthracenecarboxylate (AAC);
FIG. 2 is a photograph of AAC obtained in example 11H NMR spectrum;
FIG. 3 is a photograph of AAC obtained in example 113C NMR spectrum;
FIG. 4 is a graph showing infrared spectrum tracing in example 1Photo-reversible adhesives (DAAC) based on anthracene groups1) The infrared spectrogram of the curing process, the curves 4a to 4d are the infrared spectrograms of 0s, 20s, 1min and 5min of ultraviolet irradiation in sequence;
FIG. 5 is a graph showing UV spectra of DAACs obtained in examples 1 and 2, which were monitored by UV spectroscopy, wherein curve 5a1And 5a2Are respectively DAAC1And DAAC2UV-Vis spectrum for decrosslinking at 254nm UV, Curve 5b1And 5b2Are respectively DAAC1And DAAC2UV-visible spectrum of re-crosslinking at 365 nm;
FIG. 6 is a DSC curve of DAAC obtained in examples 1 and 2 and that obtained when the DAAC is uncrosslinked and then uncrosslinked, curve 6a1And 6a2Are respectively DAAC1And DAAC2DSC curve of (1), curve 6b1And 6b2Are respectively DAAC1And DAAC2DSC curve at uncrosslinking, Curve 6c1And 6c2Are respectively DAAC1And DAAC2DSC curve upon re-crosslinking;
FIG. 7 is a tensile shear test curve, curve 7a, of the DAAC obtained in examples 1 and 21、7a2、7a3DAACs obtained in example 11Tensile shear test curve of UV photolytic crosslinking, UV re-crosslinking, 7b1、7b2、7b3DAACs obtained in example 2 were each obtained2A tensile shear test curve of ultraviolet photolysis crosslinking and ultraviolet re-crosslinking;
FIG. 8 is a schematic diagram of reversible structure transformation for crosslinking-decrosslinking under DAAC UV light.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The test instruments and test conditions used in the examples were as follows:
FTIR: bruker Alpha FTIR adopts KBr tabletting method and is arranged at 4000-400 cm-1In the wavenumber range of 4cm-1At a resolution of (c).
NMR: nuclear magnetic resonance spectroscopy (1H-NMR and13C-NMR) at room temperature using CDCl3The solvent was used on a Bruker AV400MHz NMR spectrometer (Germany).
UV-vis: UV-vis spectroscopy was performed by a Shimadzu UV-2550 spectrometer in absorption mode. The solid state sample test method was used.
DSC: on a TA Instruments Q20 equipped with an RCS 90 cooling system, at N2Atmosphere (50 ml. min)-1) Next, DSC tests were performed on the original, uncrosslinked, and re-crosslinked networks. All samples were heated from-50 ℃ to 100 ℃ at a heating rate of 10 ℃/min.
Tensile shear test: tensile shear strength testing was performed at room temperature using a SANS UTM5205XHD test equipment. The bonding substrates include quartz glass and PE films using a single lap shear test method. The moving speed of the sample holder was set to 10 mm/min.
The sources of the compounds used in the examples are as follows:
name of medicine Manufacturer of the product
9-Anthraenecarboxylic acid Hadamard reagent Ltd
Allyl bromide Alphaesar (China) chemical Co., Ltd
Deionized water Self-made
N, N-dimethylformamide Taishiai (Shanghai) chemical industry development Limited
Potassium carbonate Alphaesar (China) chemical Co., Ltd
3, 6-dioxa-1, 8-octane dithiol SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd.
Trimethylolpropane tris (3-mercaptopropionate) SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd.
2-hydroxy-2-methyl acetone (1173) SHANGHAI MACKLIN BIOCHEMICAL Co.,Ltd.
Example 1
1) Preparation of anthracene-containing allylation product: dissolving 1mol of 9-anthracene carboxylic Acid (AC) raw material in 30mol of polar solvent DMF, keeping the temperature at 0 ℃ in an ice-water bath, and then adding 1.1mol of anhydrous K2CO3. After stirring for 30 minutes, 1.1mol of allyl bromide is dropped into the system at a dropping speed of 20 drops/min, and after the dropping is finished, the mixture is stirred for 24 hours at room temperature. Obtaining an allylation product containing an anthracenyl group, namely allyl 9-anthracenecarboxylate (AAC), by centrifugation, toluene extraction, rotary evaporation and drying;
2) preparation of photo-reversible adhesive containing anthracene group: 1mol of allyl 9-anthracenecarboxylate prepared in step 1) is mixed with 0.03mol of trimethylolpropane tris (3-mercaptopropionate) and 0.45mol of 3, 6-dioxa-1, 8-octane dithiol in terms of mass fractionAdding 1173 photosensitizer into 0.5%, stirring, and irradiating with ultraviolet light of more than 365nm for 5min to crosslink and solidify to obtain optically reversible adhesive (DAAC) containing anthracene group1)。
The obtained photo-reversible adhesive containing anthracene group is subjected to a tensile shear test, and the bonding strength of the photo-reversible adhesive containing anthracene group to quartz glass is 3.4MPa, the strength after photo-degradation for 15 minutes under 254nm ultraviolet irradiation is 0.73MPa, the strength after photo-degradation for 5 minutes under the ultraviolet irradiation of more than 365nm is recovered to 2.97MPa (figure 7a), the strength after photo-degradation is only 20% of the original strength, and the strength recovery rate of re-crosslinking is about 80%.
Example 2
Weighing 1mol of allylation product prepared in the step 1) of the example 1, 0.10mol of trimethylolpropane tris (3-mercaptopropionate) and 0.35mol of 3, 6-dioxa-1, 8-octane dithiol in parts by mol, mixing, adding 1173 photosensitizer in an amount of 0.5 percent by mass, uniformly stirring, and then irradiating for 5 minutes under the ultraviolet light of more than 365nm to crosslink and solidify the mixture to obtain the photo-reversible adhesive (DAAC) containing anthryl groups2)。
The resulting photo-reversible adhesive containing an anthryl group was tested for tensile shear strength and found to have an adhesive strength of 0.76MPa to a polyethylene film, a photodegradation strength of 0.17MPa after irradiation with UV light at 254nm for 15 minutes and a recovery strength of 0.60MPa after irradiation with UV light at greater than 365nm for 5 minutes (FIG. 7 b).
And (3) testing and characterizing:
1. characterization of the Infrared Spectrum
FIG. 1 is an infrared spectrum of 9-anthracenecarboxylic Acid (AC) and 9-anthracenecarboxylic acid allyl ester (AAC) in example 1, wherein a is an infrared spectrum of AC at 3000cm-1The nearby broad peak is attributed to the vibration of-OH, and after the reaction, the disappearance of the absorption can be observed, indicating that-OH is completely consumed in the reaction; b is the spectrum of AAC at 931, 993 and 1646cm-1The absorption at (A) represents-C ═ CH in the allyl radical2Indicating that the allylation reaction between allyl bromide and the-OH group has been successfully carried out.
NMR characterization of AAC
To further confirm the structure, we performed NMR characterization of AAC. FIG. 2 is of AAC1H NMR, FIG. 3 for AAC13C NMR spectrum from1It can be clearly observed in the H NMR spectrum that the peaks at 5.45 and 5.30ppm are due to the proton 8(-C ═ CH)2) The peaks at 8.36, 8.05, 7.87, 7.51-7.42 and 7.37, which are attributed to protons in the anthracene ring, can accordingly also be determined to correspond one-to-one to the peaks at 6.12 and 5.07ppm, while the peaks of carbon also coincide with the characteristic peaks of carbon in AAC, which is a good indication that AAC has been successfully synthesized.
3. Curing FTIR tracking
To obtain the optimum cure time and to confirm complete cure, the cross-linking cure process of step 2 in example 1 was followed using FTIR. The curing system was coated on a KBr sheet to form a film, and then irradiated with UV light of 365nm for various lengths of time by a high-pressure mercury lamp (100W) to obtain samples of various degrees of curing, as shown in FIG. 4. As can be seen from the figure, at 2567cm-1And 1646cm-1The peaks at (a) represent characteristic absorptions of-SH and-C ═ C, respectively, and as the ultraviolet irradiation time increased, the characteristic absorption peak of-SH was almost completely disappeared and the peak of-C ═ C was also significantly decreased, demonstrating that the photo-reversible adhesive containing an anthracenyl group obtained in example 1 achieved complete curing reaction.
De-crosslinking and re-crosslinking UV-visible Spectroscopy characterization of DAAC thiol-ene networks
UV-Vis spectroscopy can be used to monitor the photoreversibility process of the photoreversible adhesive DAAC containing anthracene groups (FIG. 5), a in FIG. 51And b1Examples 1, a2And b2Example 2 was used. The efficiency of depolymerization and repolymerization is quantitatively obtained by monitoring and comparing the change in the characteristic signal of anthracene between 320 and 420 nm. The allylated product, trithiol, and a mixture of dithiol and photoinitiator were spin coated on a quartz substrate and irradiated with 365nm uv light for 10 minutes to produce a cured film of DAAC thiol-ene network. Next, the sample was irradiated with UV light at 254nm to cause cleavage of anthracene dimer, and the UV spectrum was monitored until the spectrum no longer changed, i.e., the decrosslinking was complete. The sample was then irradiated with 365nm UV light to reform the anthracene dimerAllowing it to re-crosslink. The left panel a in FIG. 5 shows the spectrum of DAAC under 254nm irradiation, and the characteristic peak of anthracene between 320 and 420nm is obviously increased, indicating the progress of the decrosslinking reaction. The right panel b in fig. 5 is the spectrum change of DAAC when the sample was re-irradiated at 365nm, and the signal of anthracene was reduced to almost disappear in all the systems. The recovery efficiencies of DAAC-cleaved dimers at 365nm UV were calculated to be 96.2% and 95.8%, respectively, for the DAAC in example 11Thioether bonding versus DAAC in example 22The more thioether bonds, i.e., the more flexible thioether bonds, the higher the recovery efficiency.
The above-mentioned recovery rate is calculated as follows:
recovery rate ═ recovered part/undecomposed part ═ Δ ab/ΔAa＝(Aat-Abt)/(Aat-Aa0)，
Wherein A isa0And AatAbsorbance at 368nm, A, at 0s and at the time of termination t in FIG. 5a, respectivelybtThe absorbance at 368nm at the time t of the termination in the graph of FIG. 5 b.
DSC characterization of decrosslinking and re-crosslinking of DAAC thiol-ene networks
When the DAAC network is broken and de-crosslinked, free oligomers or monomers are obtained, these small segments flow easily and are then re-crosslinked and recover the original crosslinked network characteristics, during which TgIs an important characteristic parameter. The results are shown in FIG. 6, DAAC exposed to UV at 254nm2Example 2 and DAAC1Example 1T of samplegRespectively reducing the temperature from 35.54 ℃ and 32.24 ℃ before decrosslinking to-3.89 ℃ and-8.02 ℃ after decrosslinking. This effect is attributed to the cleavage of the cyclobutane structure of the crosslinked network to form small free monomers, followed by re-4 π +4 π cycloaddition with 365nm UV irradiation, resulting in the restoration of the crosslinked network structure, DAAC2And DAAC1T ofgThe temperatures were raised to 32.16 ℃ and 29.68 ℃ respectively, indicating that the DAAC obtained by repolymerization substantially restored the state of the crosslinked network before, and has strong reversible reaction capability.

Claims (10)

1. An anthracene-based group-containing photo-reversible adhesive, comprising the following structure:
Figure FDA0002480244210000011
wherein R is1And R3Optionally selected from alkyl, alkoxy or alkyl ester group with 1-20 carbon atoms, R2Is an alkoxy group or an alkyl ester group having 1 to 3 carbon atoms.
2.A method for preparing the photo-reversible adhesive containing anthracene group according to claim 1, comprising the steps of: firstly, reacting an anthracene-based compound with an allyl compound to obtain an allyl product containing anthracene-based, then adding a thiol compound and a photosensitizer, and irradiating by ultraviolet light to obtain the light reversible adhesive containing anthracene-based.
3. The method according to claim 2, comprising the steps of:
step one, dissolving an anthracene-based compound in a solvent, then adding anhydrous potassium carbonate, dropwise adding an allyl compound while stirring, and stirring for reaction to obtain an allylation product containing anthracene groups;
and step two, adding a thiol compound and a photosensitizer into the allylation product containing the anthracene group obtained in the step one, uniformly stirring, and carrying out a light irradiation reaction under ultraviolet light to obtain the light reversible adhesive containing the anthracene group.
4. The production method according to claim 3,
in the first step, the anthracene-based compound is selected from at least one of anthracene-based carboxylic acid compounds and anthracene-based alcohol compounds, preferably at least one of 9-anthracene carboxylic acid, 9-anthracene acetic acid, 9-anthracene methanol and 1- (9-anthracene-based) ethanol; and/or the presence of a gas in the gas,
the allyl compound is selected from at least one of allyl alcohol, allyl carboxylic acid and allyl halide, preferably selected from allyl halide, and more preferably selected from allyl bromide; and/or the presence of a gas in the gas,
the molar ratio of the anthracene-based compound to the anhydrous potassium carbonate to the allyl compound is 1:1: 1-1: 1.3: 1.3; and/or the presence of a gas in the gas,
the solvent is a polar solvent and is selected from at least one of tetrahydrofuran and N, N-dimethylformamide; and/or the presence of a gas in the gas,
the mass ratio of the anthracene-based compound to the solvent is 1: 5-1: 20; and/or the presence of a gas in the gas,
the stirring reaction temperature is 0-30 ℃; and/or the presence of a gas in the gas,
the stirring reaction time is 24-48 h.
5. The production method according to claim 3,
in the second step, the molecular formula of the thiol compound is R- (SH)xWherein R is selected from alkyl, alkoxy or alkyl ester group with 1-20 carbon atoms, and x is 2 or 3; and/or the presence of a gas in the gas,
the molar ratio of the allyl product containing the anthracene group to the mercapto group in the thiol compound is 1: 0.8-1: 1.2; and/or the presence of a gas in the gas,
the photosensitizer is selected from at least one of benzil compounds, alkyl benzophenone compounds and benzophenone compounds, preferably at least one of 2-hydroxy-2-methyl-1-phenyl acetone, 1-hydroxycyclohexyl phenyl ketone and benzophenone; and/or the presence of a gas in the gas,
the photosensitizer accounts for 0.5-2% of the total weight of the allylation product containing the anthracene group and the thiol compound by mass percent; and/or the presence of a gas in the gas,
the wavelength of the ultraviolet light is 350-370 nm; and/or the presence of a gas in the gas,
the illumination time of the ultraviolet light is 5-15 min.
6. The method according to claim 5, wherein the thiol compound is selected from the group consisting of a dithiol compound and a trithiol compound, wherein the dithiol compound is selected from at least one of 2, 2' - (1, 2-ethanediylbiaoxo) bisethanethiol, ethanedithiol, propanethiol, 2, 3-butanedithiol, hexanedithiol, decanedithiol, and s-triazine dithiol, and the trithiol compound is selected from at least one of trimethylolpropane tris (3-mercaptopropionate), propane-1, 2, 3-trithiol, and 1,3, 5-triazine-2, 4, 6-trithiol.
7. The preparation method according to claim 6, wherein the molar ratio of the dithiol compound to the trithiol compound is 1.5:1 to 15: 1.
8. The production method according to claim 3,
after anhydrous potassium carbonate is added in the step one, stirring in an ice-water bath until the allyl compound is completely added dropwise; and/or the presence of a gas in the gas,
the dropping speed of the allyl compound is 10-30 drops/min; and/or the presence of a gas in the gas,
and (2) centrifuging, extracting, performing rotary evaporation and drying the allyl product containing the anthracene group obtained in the first step, wherein a solvent adopted in the extraction is at least one of toluene, chloroform and carboxylic ester.
9. The photo-reversible adhesive according to claim 1 or the photo-reversible adhesive obtained by the preparation method according to any one of claims 2 to 8, wherein the photo-reversible adhesive realizes reversible structure conversion of crosslinking-decrosslinking under the action of ultraviolet light.
10. The photo-reversible adhesive as claimed in claim 9, wherein the photo-reversible adhesive is crosslinked at an ultraviolet wavelength of 350 to 370nm and is uncrosslinked at an ultraviolet wavelength of 220 to 280 nm.
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