CN115960103A - Tropinone-based conjugated ketene derivative and preparation method and application thereof - Google Patents
Tropinone-based conjugated ketene derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a tropinone conjugated ketene derivative and a preparation method and application thereof. The structural formula of the tropinone-based conjugated ketene derivative is as follows:
the preparation method comprises the steps of mixing and reacting dialkoxy substituted benzaldehyde, tropinone, a solvent and an alkali solution, cooling, filtering, washing with water and drying to obtain the tropinone-based conjugated ketene derivative, wherein the reaction temperature is 20-80 ℃, and the reaction time is 6-12 hours; the prepared product has strong adhesive property, and under the irradiation of a light source of 200-700 nm, the absorbed light energy of the solid tropinone-based conjugated ketene can be used as heat energy to melt the tropinone-based conjugated ketene into liquid and lose the adhesive property, thereby realizing the effect of light-operated debonding; the light-operated debonding adhesive is easy to synthesize and clean, and can realize efficient light-operated debondingAnd (4) sticking.
Description
Technical Field
The invention relates to the technical field of adhesive materials, in particular to a tropinone-based conjugated ketene derivative and a preparation method and application thereof.
Background
An adhesive is a substance that connects two materials together by the adhesive and cohesive strength of the interface. Adhesives have found widespread use in both everyday life and in industrial manufacturing. Debonding, cleaning, and bonding of adhesives is also important in the assembly and disassembly of temporary structures.
Chinese patent CN104812859A discloses a heat debondable adhesive article, applicant 3M innovative limited, but in some cases, local heating presents difficulties. The light has the advantages of no contact and space-time controllability, and the realization of debonding by changing the bonding performance of the adhesive through illumination has important academic value and practical application value. Chinese patent CN108774151A discloses an azobenzene derivative for realizing solid-liquid transformation based on photo-thermal induction, a preparation method thereof and application thereof as an optical switch adhesive, wherein the compound can realize photo-thermal solid-liquid transformation to realize debonding under green light, but the azobenzene derivative optical debonding agent reported in the patent needs multi-step synthesis and has higher cost, the melting point of the azobenzene derivative optical debonding agent is about 44 ℃, which means that the use environment of the azobenzene derivative optical debonding agent cannot be higher than 44 ℃, and the application range is limited.
Therefore, it is necessary to develop an optical switch adhesive which is low in cost, can be used in a wide temperature range, and is easy to debond and clean.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention provides a tropinone-based conjugated ketene derivative and a preparation method and application thereof.
The conjugated ketene compounds are small molecular dyes, can be prepared by utilizing the claisen Schmidt condensation reaction between specific aldehyde and ketone, and have high adjustability in light absorption capacity, melting point and crystallization capacity due to wide synthetic raw materials. Under illumination, the conjugated ketene compounds hardly emit light, and most of light energy is converted into heat energy. The properties enable the conjugated ketene compounds to have potential to realize solid-liquid phase transformation through photo-thermal effect, wherein the solid state corresponds to the state of high bonding force of the adhesive, and the liquid state corresponds to the state of weak bonding force of the adhesive. However, no technical literature has been reported on the use of conjugated ketene compounds as binders for light-controlled debonding. Therefore, the development of the light-operated debonding adhesive of the conjugated ketene derivative, which has low cost, adjustable melting point and crystallization property and photo-thermal phase conversion property, has good application prospect in the field of bonding.
The method uses tropinone and benzaldehyde with a dialkoxyl chain to obtain the final tropinone conjugated ketene derivative through one-step claisen Schmidt condensation. The melting point of the prepared conjugated ketene is adjusted within 100 ℃ by adjusting the length of the alkyl chain. The obtained tropinone-based conjugated ketene is yellow crystal and has strong adhesive property. Under the irradiation of a light source of 200-700 nm, the solid tropinone conjugated ketene takes absorbed light energy as heat energy to melt the tropinone conjugated ketene into liquid, so that the bonding performance is lost.
The light-operated debonding adhesive is easy to synthesize and clean, can realize efficient light-operated debonding, and is convenient to use and debonding as required.
One object of the present invention is to provide a tropinone-conjugated ketene derivative.
The structural formula of the tropinone-based conjugated ketene derivative is as follows:
wherein n is any integer of 2 to 12; n is preferably 5, 6, 7 or 8;
when n is 5, 6, 7, 8, the compound has proper melting point and crystallization rate, so that the compound is beneficial to realizing photothermal phase conversion and being used as a bonding agent;
the tropinone-based conjugated ketene derivative has the property of photo-thermal solid-liquid phase transition.
Another object of the present invention is to provide a method for preparing a troponyl conjugated enone derivative, comprising:
mixing and reacting dialkoxy substituted benzaldehyde, tropinone, a solvent and an alkali solution, cooling, filtering, washing with water and drying to obtain the tropinone-based conjugated ketene derivative;
the reaction temperature is 20-80 ℃; preferably 50-70 ℃;
the reaction time is 6-12 h; preferably 8-10 h;
the solvent comprises a solvent A and a solvent B;
the tropinone-based conjugated ketene derivative is obtained by one-step reaction of tropinone and dialkoxy-substituted benzaldehyde, heating conditions are preferably adopted in the reaction, a crude product is separated out after cooling reaction liquid, namely, the crude product is subjected to primary recrystallization, after the reaction is finished, the crude product is cooled to room temperature, yellow precipitate is separated out, the solid product is filtered and washed to be neutral by deionized water, and the tropinone-based conjugated ketene derivative with higher purity can be obtained after vacuum drying.
In a preferred embodiment of the present invention,
uniformly mixing dialkoxy substituted benzaldehyde, a solvent A and an alkali solution to prepare a mixture, dissolving tropinone in a solvent B to prepare a tropinone solution, dripping the tropinone solution into the mixture for reaction, and then cooling, filtering, washing and drying to obtain the tropinone-based conjugated ketene derivative;
the method of firstly mixing the dialkoxy substituted benzaldehyde, the alkali solution catalyst and the solvent A and then dripping the tropinone solution into the mixture is favorable for the complete reaction of the tropinone.
In a preferred embodiment of the present invention,
the structural formula of the dialkoxy substituted benzaldehyde is as follows:
wherein n is any integer of 2 to 12; n is preferably 5, 6, 7 or 8;
the tropinone has the structural formula:
in a preferred embodiment of the present invention,
the molar ratio of the dialkoxy substituted benzaldehyde to tropinone is (2-3): 1; and/or the presence of a gas in the atmosphere,
the molar ratio of the alkali to the tropinone is (1-5): 1; and/or the presence of a gas in the atmosphere,
the mass ratio of the solvent A to the dialkoxy substituted benzaldehyde is (10-50): 1; and/or the presence of a gas in the gas,
the mass ratio of the solvent B to the tropinone is (5-20): 1.
in a preferred embodiment of the present invention,
the molar ratio of the dialkoxy substituted benzaldehyde to tropinone is (2-2.2): 1; and/or the presence of a gas in the gas,
the molar ratio of the alkali to the tropinone is (2-4): 1; and/or the presence of a gas in the gas,
the mass ratio of the solvent A to the dialkoxy substituted benzaldehyde is (30-40): 1; and/or the presence of a gas in the gas,
the mass ratio of the solvent B to the tropinone is (10-15): 1.
in a preferred embodiment of the present invention,
the solvent A and the solvent B are respectively and independently selected from one of methanol, ethanol, isopropanol and tert-butyl alcohol; and/or the presence of a gas in the atmosphere,
the alkali solution is an organic alkali solution or an inorganic alkali solution.
In a preferred embodiment of the present invention,
the organic base is at least one of sodium ethoxide, sodium methoxide and potassium tert-butoxide;
the inorganic base is at least one of sodium hydroxide, potassium carbonate, potassium hydroxide, lithium hydroxide and ammonium hydroxide;
the solvent in the alkali solution is water or ethanol;
the concentration of the alkali solution is 0.02 g/mL-0.25 g/mL.
The invention also provides a tropinone conjugated ketene derivative prepared by the method.
The invention also provides the application of the tropinone-based conjugated ketene derivative in the adhesive for light-operated debonding.
The tropinone-based conjugated ketene derivative with the photothermal solid-liquid phase conversion characteristic can be used for an adhesive for light-operated debonding.
The solid optical switch adhesive with the bonding performance can absorb light energy and convert the light energy into heat under the irradiation of a light source with the wavelength of 200-700 nm, and the rise of the temperature causes the tropinone-based conjugated ketene to be melted into liquid state and lose the bonding performance; preferably 405 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) The tropinone-based conjugated ketene derivative is synthesized, is applied to the adhesive for light-operated debonding, and achieves good effect;
(2) The tropinone-based conjugated ketene derivative synthesized by the method has strong absorption in near ultraviolet and visible light regions, can efficiently convert light energy into heat energy, has excellent photo-thermal effect, and can generate solid-liquid phase conversion under the irradiation of a light source of 200-700 nm due to the photo-thermal effect so as to realize the effect of light-operated debonding;
(3) The tropinone-based conjugated ketene light-operated adhesive with the photo-thermal phase transition characteristic has strong adhesive force in a solid state, the melting point is 75-95 ℃, and the adhesive force can be kept in a wider temperature range compared with the prior art;
(4) The tropinone-based conjugated ketene derivative synthesized by the method is easy to dissolve in common organic solvents such as dichloromethane and the like, and is easy to clean after being de-bonded;
(5) The synthetic method of the tropinone-based conjugated ketene derivative has simple synthetic steps, does not need purification, and has good commercial prospect.
Drawings
FIG. 1 is an absorption spectrum of the tropinone-based conjugated ketene prepared in examples 1 to 4;
examples 1-4 have similar light absorption capabilities, with example 3 having a slightly higher light absorption capability, with peak positions of maximum absorption wavelengths being substantially the same, as shown by the higher degree of curve overlap on the graph;
FIG. 2 is a DSC chart of the tropinone-based conjugated ketene prepared in examples 1-4;
the numbers marked in the figures are melting points;
FIG. 3 is a graph showing the temperature change of the tropinone-based conjugated ketene powders prepared in examples 1 to 4 under the irradiation of an LED light source of 405 nm;
the blank is a polytetrafluoroethylene plate;
examples 1-4 have similar photothermal properties, and are shown on the graph as higher curve overlap;
FIG. 4 is a photograph showing the tropinone-based conjugated ketene powder prepared in example 2 after being irradiated by an LED light source at 405nm for 1 minute;
most of the powder in the figure becomes liquid;
FIG. 5 is a photograph showing the tropinone-based conjugated ketene powder prepared in example 4 after being irradiated by an LED light source at 405nm for 1 minute;
only the surface powder in the figure becomes liquid;
FIG. 6 is a photograph of the tropinone-based conjugated ketene prepared in example 1 after being bonded to glass;
in the figure, 2mg of the tropinone-based conjugated ketene prepared in example 1 was used to horizontally bond two pieces of glass, and the bonding area was 1.6cm 2 A weight is hung at one unbonded end of 1 glass, and a spring balance is used for measuring the unbonded end of the other 1 glass, so that a weight of 5kg can be lifted in the actual measurement.
Detailed Description
While the present invention will be described in detail and with reference to the specific embodiments thereof, it should be understood that the following detailed description is merely illustrative of the present invention and should not be taken as limiting the scope of the present invention, but is intended to cover modifications and variations thereof that would occur to those skilled in the art upon reading the present disclosure.
The bis-alkoxy-substituted benzaldehydes used in the examples were synthesized by laboratory personnel, reference being made to: facility Bottom-Up Synthesis of Coronene-based 3-Fold symmetry and high Bottom synthesized Nanogliptenes from Simple aromatics J.Am.chem.Soc.2014,136,5057-5064 (translation: bottom-Up Synthesis from Simple aromatics based on the triple symmetry and Highly Substituted nanopatterns of Kelong).
Synthesis of bis-alkoxy-substituted benzaldehydes:
a mixture of 3, 4-dihydroxybenzaldehyde (10 mmol), anhydrous potassium carbonate (40 mmol) and n-bromoalkane (22 mmol) was added to 50mL of N, N-dimethylformamide and reacted at 85 ℃ for 24 hours with magnetic stirring; after completion of the reaction, the reaction mixture was poured into 100mL of deionized water, extracted with dichloromethane (20 mL × 3), the dichloromethane phases were combined, washed 3 times with a saturated aqueous sodium chloride solution (20 mL × 3), dried over night with anhydrous sodium sulfate, and concentrated; the crude product is purified by column chromatography, eluting with petroleum ether and ethyl acetate (volume ratio 20.
The test method comprises the following steps:
testing a photo-thermal heating curve: 20mg of the example compound are placed in a metallic aluminum plate and irradiated with a 405nm LED light source (800 mW/cm) 2 ) The temperature change during the illumination was monitored using an infrared thermal imager FLIR-E6.
Melting point test of the compounds: placing 2-10 mg of a sample to be detected in a metal aluminum plate, monitoring the position of a melting peak by using a differential scanning calorimeter (Mettlerlatido), and taking the position of the melting peak when the second circle is heated as the melting point of the sample;
and (3) testing the bonding performance: placing a certain amount of sample to be tested on a clean glass sheet, heating the clean glass sheet by a hot platform to melt the sample, covering the other glass sheet on the liquid level, applying certain pressure to enable the two glass sheets to be tightly attached, then cooling the glass sheets at room temperature for 30 minutes to enable the two glass sheets to be fully crystallized, and then loading a heavy object on the glass sheets to test;
light-operated debonding experiment: placing 2mg of sample to be measured on a clean glass sheet, heating the clean glass sheet by a hot stage to melt the sample, covering the other glass sheet on the liquid surface, applying certain pressure to enable the two glass sheets to be tightly attached, then cooling the glass sheet at room temperature for 30 minutes to enable the glass sheet to be fully crystallized, loading a 1kg weight on the bonded glass sheet, and using 405nm LED light (800 mW/cm) 2 ) The bonding area was irradiated and the time required for the two bonded pieces of glass to separate was recorded.
Example 1
3, 4-bis (pentyloxy) benzaldehyde (10mmol, 2.78g) was charged in a 250mL three-necked flask, 85g of ethanol was added, the mixture was stirred at 50 ℃ to dissolve the benzaldehyde, and an aqueous solution of sodium hydroxide ((20mmol, 0.8g)/4 mL of H was slowly added 2 O); dissolving tropinone (5mmol, 0.70g) in 7g of ethanol, and slowly dripping tropinone solution into the benzaldehyde solution at 50 ℃ by using a dropping funnel within 1h, wherein the total reaction time is 8h (including dripping time); and cooling to room temperature after complete reaction, precipitating the product, filtering to obtain a crude product, washing the precipitate with deionized water to neutrality, drying to obtain a target product, and obtaining the tropinone-based conjugated ketene derivative without further purification, wherein the tropinone-based conjugated ketene derivative can be directly used as an adhesive.
Obtaining structural characterization data of the tropinone conjugated ketene derivative:
1 H NMR(400MHz,CDCl 3 )δ7.79(s,2H),7.02–6.86(m,6H),4.48(s,2H),4.04(q,J＝6.8Hz,8H),2.63(s,2H),2.35(s,3H),2.04(d,J＝7.1Hz,2H),1.91–1.76(m,8H),1.52–1.34(m,16H),0.94(td,J＝7.1,1.0Hz,12H).
wherein the peak at the chemical shift of 7.79-6.86 ppm is the hydrogen of benzene ring and trans double bond; the single peak at a chemical shift of 2.35ppm is the hydrogen on the N-methyl group on the tropinone ring; hydrogen on a tertiary carbon in a unimodal piperidone ring with a chemical shift at 4.48 ppm; the hydrogens at chemical shifts 2.63ppm and 2.04ppm are on the adjacent two methylenes within the piperidone ring; the remaining off-peak can be attributed to the hydrogen of the alkoxy chain; and (3) confirming that the target product has a correct structure through the integration and peak attribution of a nuclear magnetic hydrogen spectrum.
Example 2
3, 4-di (hexyloxy) benzaldehyde (11 mmol,3.37 g) was charged into a 500mL three-necked flask, 130g of ethanol was added, the mixture was heated and stirred at 60 ℃ to dissolve the ethanol, and an aqueous solution of sodium hydroxide ((10 mmol,0.4 g)/16 mLH) was slowly added 2 O); dissolving tropinone (5mmol, 0.70g) in 10g ethanol, and slowly dripping tropinone solution into the benzaldehyde solution at 60 ℃ within 1h by using a dropping funnel, wherein the total reaction time is 10h (including dripping time); and cooling to room temperature after complete reaction, precipitating the product, filtering to obtain a crude product, washing the precipitate with deionized water to neutrality, and drying to obtain a target product, wherein the target product is the tropinone-based conjugated ketene derivative without further purification and can be directly used as an adhesive.
Obtaining structural characterization data of the target product:
1 H NMR(400MHz,CDCl 3 )δ7.78(s,2H),7.05–6.80(m,6H),4.47(s,2H),4.03(q,J＝6.8Hz,8H),2.62(s,2H),2.34(s,3H),2.04(d,J＝7.1Hz,2H),1.90–1.77(m,8H),1.48(dd,J＝12.8,6.9Hz,8H),1.35(dd,J＝4.7,2.3Hz,16H),0.91(dd,J＝7.0,5.8Hz,12H).
wherein the peak at the chemical shift of 7.78-6.80 ppm is the hydrogen of benzene ring and trans double bond; the single peak at a chemical shift of 2.34ppm is the hydrogen on the N-methyl group on the tropinone ring; hydrogen on a tertiary carbon in a unimodal piperidone ring with a chemical shift at 4.47 ppm; the hydrogens at chemical shifts 2.62ppm and 2.04ppm are on the adjacent two methylenes within the piperidone ring; the remaining off-peak can be attributed to the hydrogen of the alkoxy chain; and (3) confirming that the target product has a correct structure through the integration and peak attribution of a nuclear magnetic hydrogen spectrum.
Example 3
3, 4-bis (octyloxy) benzaldehyde (10mmol, 3.62g) was charged in a 500mL three-necked flask, 125g of isopropyl alcohol was added, the mixture was dissolved by heating and stirring at 65 ℃ and an aqueous solution of sodium hydroxide ((15mmol, 0.6g)/6 mL of H was slowly added 2 O); tropinone (5 mmol, 0.70g) was dissolved in 7g ethanol and the tropinone solution was added to the mixture at 65 ℃ using a dropping funnelSlowly dripping the mixture into the benzaldehyde solution within 1h, wherein the total reaction time is 9h (including dripping time); and cooling to room temperature after complete reaction, precipitating the product, filtering to obtain a crude product, washing the precipitate with deionized water to neutrality, and drying to obtain a target product, wherein the target product is the tropinone-based conjugated ketene derivative without further purification and can be directly used as an adhesive.
Obtaining structural characterization data of a target product:
1 H NMR(400MHz,CDCl 3 )δ7.79(s,2H),7.02–6.88(m,6H),4.48(s,2H),4.03(q,J＝6.8Hz,8H),2.63(s,2H),2.35(s,3H),2.04(d,J＝7.0Hz,2H),1.88–1.79(m,8H),1.47(dd,J＝13.6,6.8Hz,8H),1.41–1.26(m,32H),0.89(t,J＝6.6Hz,12H).
wherein the peak at the chemical shift of 7.79 to 6.88ppm is the hydrogen of the benzene ring and the trans double bond; the single peak at a chemical shift of 2.35ppm is the hydrogen on the N-methyl group on the tropinone ring; a hydrogen on a tertiary carbon in the unimodal piperidone ring with a chemical shift at 4.48 ppm; the hydrogens at chemical shifts 2.63ppm and 2.04ppm are on the adjacent two methylene groups within the piperidone ring; the remaining off-peak can be attributed to the hydrogen of the alkoxy chain; and (3) confirming that the target product has a correct structure through the integration and peak attribution of a nuclear magnetic hydrogen spectrum.
Example 4
3, 4-Didodecyloxy benzaldehyde (10mmol, 4.75g) was put into a 500mL three-necked flask, 140g of methanol was added, the mixture was stirred at 70 ℃ to dissolve the benzaldehyde, and an ethanol solution of potassium tert-butoxide ((15mmol, 1.68g)/10 mL of ethanol) was slowly added; dissolving tropinone (5mmol, 0.70g) in 10g ethanol, and slowly dripping tropinone solution into the above benzaldehyde alkali solution at 70 ℃ by using a dropping funnel within 1h, wherein the total reaction time is 9h (including dripping time); and cooling to room temperature after complete reaction, precipitating the product, filtering to obtain a crude product, washing the precipitate with deionized water to neutrality, and drying to obtain a target product, wherein the target product is the tropinone-based conjugated ketene derivative without further purification and can be directly used as an adhesive.
Obtaining structural characterization data of the target product:
1 H NMR(400MHz,CDCl 3 )δ7.78(s,2H),7.01–6.87(m,6H),4.47(s,2H),4.03(q,J＝6.7Hz,8H),2.62(s,2H),2.34(s,3H),2.03(d,J＝7.1Hz,2H),1.89–1.78(m,8H),1.47(dd,J＝13.2,6.8Hz,8H),1.38–1.24(m,64H),0.88(t,J＝6.8Hz,12H).
wherein the peak at the chemical shift of 7.78-6.87 ppm is the hydrogen of benzene ring and trans double bond; the single peak at a chemical shift of 2.34ppm is the hydrogen on the N-methyl group on the tropinone ring; a hydrogen on a tertiary carbon in the unimodal piperidone ring with a chemical shift at 4.47 ppm; the hydrogens at chemical shifts 2.62ppm and 2.03ppm are on the adjacent two methylenes within the piperidone ring; the remaining hydrogen that can be assigned to the alkoxy chain; and (3) confirming that the target product has a correct structure through the integration and peak attribution of a nuclear magnetic hydrogen spectrum.
The photothermal temperature rise curve test, the compound melting point test, the adhesion performance test and the light-operated debonding test were performed on examples 1 to 4, respectively.
FIG. 1 shows the absorption spectrum of the troponyl conjugated ketene prepared in examples 1 to 4, and as shown in FIG. 1, examples 1 to 4 all have strong absorption at 250nm to 700 nm.
FIG. 3 is a graph showing the temperature change of the tropinone-based conjugated ketene powders prepared in examples 1 to 4 under irradiation of a 405nm LED light source, and as shown in FIG. 3, the temperature of the powders of examples 1 to 4 can be raised to about 110 ℃ after 5 minutes under irradiation of the 405nm LED light source.
As can be seen from fig. 1 and fig. 3, the change of the alkyl chain has little influence on the light absorbing ability and the photothermal conversion ability of the tropinone-based conjugated ketene;
FIG. 2 is a DSC chart of the tropinone-based conjugated ketenes prepared in examples 1-4, as shown in FIG. 2, the melting points of examples 1-4 are 83.2 deg.C, 74.9 deg.C, 82.6 deg.C, 94.7 deg.C, respectively; it is shown that the change of the alkyl chain length significantly affects the melting point of the compound, and the realization of the photothermal solid-liquid conversion requires that the heat energy generated after the compound absorbs light is enough to heat the compound to be above the melting point, so the high or low melting point affects the debonding efficiency of the compound. As in example 2, the debonding required only 1 minute and 30 seconds of light, whereas example 4 required 8 minutes and 30 seconds of light under the same conditions for debonding.
Fig. 4 and 5 are photographs of the tropinone-based conjugated ketene powders prepared in example 2 and example 4 after being irradiated for 1 minute by an LED light source of 405nm, respectively, and it can be seen that most of the powders in example 2 become liquid, but only the surface layer powder in example 4 becomes liquid, because the melting point of example 4 is high, and thus the light irradiation for 1 minute is insufficient to melt the entire powder.
FIG. 6 is a photograph showing the glass bonded with the tropinone-conjugated ketene prepared in example 1, and as shown in FIG. 6, when 2mg of the adhesive of example 1 was used, a weight of 5kg was lifted; in the tests of examples 2 to 4, a weight of 5kg can be lifted in the same manner;
in the light-operated debonding experiment, when the product prepared in examples 1 to 4 was used and a weight of 1kg was loaded on a 2mg bonded glass plate, the bonding area was illuminated with a 405nm LED light source, and after 3 minutes, 1 minute 30 seconds, 3 minutes 10 seconds, and 8 minutes 30 seconds of each of examples 1 to 4, the sample between the two glass plates became liquid, and the weight fell off; in contrast, the samples of examples 1 to 4, which were not irradiated with light, were loaded with a 1kg weight for 24 hours without being debonded.
Examples 1 to 4 in the respective 20 degrees C, 30 degrees C, 40 degrees C, 50 degrees C, 60 degrees C, 70 degrees C environment, 2mg example 1 as the adhesive bonding two glass sheets can load 1kg weight 24 hours without debonding, show that the adhesive provided by the invention can be used in a wide temperature range. Example 4 can be loaded with a 1kg weight for 24 hours at 80 c without debonding because example 4 has a melting point of 94.7 c and thus remains a strong solid bond at 80 c.
The adhesive provided by the invention can be easily cleaned by immersing the glass sheets after the debonding of examples 1-4 in dichloromethane.
In general, the tropinone-based conjugated ketene compound prepared by the invention has better adhesive capacity to glass, and a sample of 2mg can be loaded with a weight of 5kg when being used as an adhesive. In terms of light-operated debonding efficiency, the melting point is lower when n =5, 6, 7 or 8, which is beneficial to realizing rapid light-operated debonding; when n is less than 5 or n is greater than 8, the melting point of the compound is high, and the light-operated debonding efficiency is reduced.
Claims (10)
1. A tropinone-based conjugated ketene derivative, characterized in that:
the structural formula of the tropinone-based conjugated ketene derivative is as follows:
wherein n is any integer of 2 to 12; n is preferably 5, 6, 7 or 8.
2. A process for the preparation of the tropinone-conjugated enone derivative according to claim 1, characterized in that the process comprises:
mixing and reacting dialkoxy substituted benzaldehyde, tropinone, a solvent and an alkali solution, cooling, filtering, washing with water and drying to obtain the tropinone conjugated ketene derivative;
the reaction temperature is 20-80 ℃; preferably 50-70 ℃;
the reaction time is 6-12 h; preferably 8-10 h;
the solvent comprises a solvent A and a solvent B.
3. The process for producing a tropinone-conjugated enone derivative according to claim 2, wherein:
uniformly mixing dialkoxy substituted benzaldehyde, a solvent A and an alkali solution to prepare a mixture, dissolving tropinone in a solvent B to prepare a tropinone solution, dripping the tropinone solution into the mixture for reaction, and then cooling, filtering, washing and drying to obtain the tropinone-based conjugated ketene derivative.
4. The process for producing a troponyl conjugated enone derivative according to claim 2, wherein:
the structural formula of the dialkoxy substituted benzaldehyde is as follows:
wherein n is any integer of 2 to 12; n is preferably 5, 6, 7 or 8.
5. The process for producing a troponyl conjugated enone derivative according to claim 2, wherein:
the molar ratio of the dialkoxy substituted benzaldehyde to tropinone is (2-3): 1; and/or the presence of a gas in the gas,
the molar ratio of the alkali to the tropinone is (1-5): 1; and/or the presence of a gas in the gas,
the mass ratio of the solvent A to the dialkoxy substituted benzaldehyde is (10-50): 1; and/or the presence of a gas in the gas,
the mass ratio of the solvent B to the tropinone is (5-20): 1.
6. the process for producing a troponyl conjugated enone derivative according to claim 5, wherein:
the molar ratio of the dialkoxy substituted benzaldehyde to tropinone is (2-2.2): 1; and/or the presence of a gas in the gas,
the molar ratio of the alkali to the tropinone is (2-4): 1; and/or the presence of a gas in the gas,
the mass ratio of the solvent A to the dialkoxy substituted benzaldehyde is (30-40): 1; and/or the presence of a gas in the gas,
the mass ratio of the solvent B to the tropinone is (10-15): 1.
7. the process for producing a tropinone-conjugated enone derivative according to claim 2, wherein:
the solvent A and the solvent B are respectively and independently selected from one of methanol, ethanol, isopropanol and tert-butyl alcohol; and/or the presence of a gas in the gas,
the alkali solution is an organic alkali solution or an inorganic alkali solution.
8. The process for producing a troponyl conjugated enone derivative according to claim 7, wherein:
the organic base is at least one of sodium ethoxide, sodium methoxide and potassium tert-butoxide;
the inorganic base is at least one of sodium hydroxide, potassium carbonate, potassium hydroxide, lithium hydroxide and ammonium hydroxide;
the solvent in the alkali solution is water or ethanol;
the concentration of the alkali solution is 0.02 g/mL-0.25 g/mL.
9. A tropinone-conjugated enone derivative prepared by the process as claimed in any one of claims 2 to 8.
10. Use of the tropinone-based conjugated ketene derivative according to claim 1 or of the tropinone-based conjugated ketene derivative prepared according to the process of one of claims 2 to 8 in an adhesive for light-controlled debonding.
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