CN114058361B - Preparation method of organic gel with photochromism and fluorescence - Google Patents

Preparation method of organic gel with photochromism and fluorescence Download PDF

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CN114058361B
CN114058361B CN202111410488.1A CN202111410488A CN114058361B CN 114058361 B CN114058361 B CN 114058361B CN 202111410488 A CN202111410488 A CN 202111410488A CN 114058361 B CN114058361 B CN 114058361B
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顾志国
高洁
晏晓东
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    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
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Abstract

The invention discloses a preparation method of an organic gel with photochromism and fluorescence, which has excellent mechanical property, transparency and adhesion property, can realize reversible blue and yellow conversion under 254nm ultraviolet light and visible light, can be recycled for at least five times, and has low photochemical loss rate. Blue fluorescence can be emitted under 365nm ultraviolet light, and the fluorescence spectrum diagrams of the organic gel before and after 254nm ultraviolet light irradiation are measured, so that the organic gel has different fluorescence intensities before and after the gel photochromic reaction. The photochromic fluorescent organic gel based on imine bonds, which is prepared by the invention, not only has excellent photochromic and photoluminescent properties, but also has great potential in the aspect of the structure of functional soft materials, and is widely applied to the fields of information storage and the like.

Description

Preparation method of organic gel with photochromism and fluorescence
Technical Field
The invention relates to the field of organogels, in particular to a preparation method of an organogel with photochromism and fluorescence.
Background
The gel is a three-dimensional cross-linked network structure which can fix solvent molecules in network gaps to form a multi-element system with high viscoelasticity. As a "soft substance", from the beginning of discovery, has received a great deal of attention from chemists, and has been used in various fields. Currently, gel chemistry is more prone to "intelligent" development. They respond correspondingly, such as volume, color, equality, under external stimuli of temperature, pH, light, redox agents, solvents, chemicals, electromagnetic fields, mechanical forces, etc. Therefore, intelligent gels attract more and more attention of scientists, and various gels with stimulus response properties are designed and researched, and then are well applied to the fields of chemical converters, memory element switches, sensors, artificial tissue muscles, chemical memories, molecular separation systems, fixation of active enzymes, tissue engineering, drug carriers, liquid crystal displays and the like.
The photoresponsive soft material has been applied to life and material science fields, such as flexible sensors, photoelectric devices, information storage and anti-counterfeiting, and biomedicine, because of its excellent optical properties and unique flexible characteristics. In particular, the luminescent hydrogel-based 3D code prepared in an environmentally friendly process can not only improve the information density per unit area, but also be used as a wearable device. On the other hand, information recorded directly in these materials is generally visible under ambient or ultraviolet light, which can prevent their practical use in confidential information protection, as these anti-counterfeit labels are easily imitated. In this case, smart materials that can sense and react to ambient stimuli are ideal choices for confidential information protection. The luminous output of these materials can be precisely modulated under external stimuli to prevent theft or imitation of the information. Stimulus responsive gels are receiving increasing attention for their additional function. They undergo reversible physical and chemical changes when exposed to external stimuli such as temperature, pH, electricity, light, and/or magnetic fields. The light responsive gel may be achieved by incorporating photochromic and/or fluorescent units into the polymer network. The preparation of gels with multiple light response characteristics is one of the hot topics in the field of material science and still has challenges.
Disclosure of Invention
The invention aims to provide a preparation method of a photochromic fluorescent multifunctional organic gel based on imine bonds, which has excellent optical characteristics and can be used for the advantage of the information storage field.
The technical aim of the invention is realized by the following technical scheme:
an organogel having photochromism and fluorescence, comprising the structure:
Figure BDA0003373673600000021
R 1 ：-CH 3 R 2 ：-C 2 H 5 R 3 ：-C 4 H 9 R 4 ：-C 6 H 13 R 5 ：-C 8 H 17 ；
the method for preparing the organogel comprises the following steps:
d1, dissolving the light-variable units and the light-emitting units in CHCl 3 In (a) and (b);
d2, dropwise adding a siloxane polymer, stirring the reaction mixture by using a magnetic stirring rod, and heating in an oil bath to obtain a yellow solution;
d3, evaporating the solvent at 50 ℃ to obtain yellow optical crosslinked polymer organogel;
and D4, carrying out ultraviolet light illumination detection on the yellow optical crosslinked polymer organic gel, wherein the structural change from ring opening to ring closing occurs under the ultraviolet light illumination, the color is changed from pale yellow to deep blue, and the color of the gel can be recovered after the visible light illumination, so that the gel has good photochromic performance.
Further set up: the light-emitting unit is one of 2, 5-dimethoxy terephthalaldehyde, 2, 5-diethoxy terephthalaldehyde, 2, 5-dibutoxy terephthalaldehyde, 2, 5-dihexyloxy terephthalaldehyde or 2, 5-bis (octyloxy) terephthalaldehyde.
Further set up: the heating reaction in the step D2 is an imine condensation reaction, provided that the reaction is carried out for 2 hours at 50 ℃.
Further set up: the photochromic unit is a perfluorocyclodiarylethene.
In summary, the invention has the following beneficial effects: the organic gel has high transparency and adhesiveness, and can be applied to information storage due to the characteristics of the photochromic fluorescent organic gel with imine bonds, so that the organic gel not only has excellent photochromic and photoluminescent properties, but also has great potential in the aspect of the structure of functional soft materials, and can be widely applied to the fields of information storage and the like, and meanwhile, the temperature required by the experiment of the preparation method is 50 ℃, and the reaction condition is relatively mild and safe; the reaction time is 2 hours, the reaction time is quick, no catalyst exists, the catalyst can be recycled, and the reaction condition is simple and convenient.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic diagram of the synthesis of a process for preparing an imine bond based photochromic fluorescent organogel 1-1;
FIG. 2 shows the structural changes during the photochromic process of organogel 1-1;
FIG. 3 is a schematic diagram of the synthesis of the preparation of an imine bond based photochromic fluorescent organogel 1-2;
FIG. 4 shows the structural changes during the photochromic process of organogel 1-2;
FIG. 5 is an infrared spectrum of an imine bond-based photochromic fluorescence organogel 1-1 prepared in example 1
FIG. 6 is an ultraviolet spectrum of an imine bond based photochromic fluorescent organogel 1-1 prepared in example 1;
FIG. 7 is a fluorescence spectrum of the imine bond based photochromic fluorescent organogel 1-1 prepared in example 1.
Detailed Description
The following describes the embodiments of the present invention further with reference to the drawings.
The technical scheme adopted by the invention is as follows:
example 1
The preparation method of the photochromic fluorescence organogel based on the imine bond comprises the following steps:
1, 2-bis (5-formyl-2-methylthiophene-3-yl) perfluorocyclopentene (31.8 mg,0.075 mmol) and 2, 5-dimethoxy terephthalaldehyde (16.67 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 Subsequently, the siloxane polymer (1.00 g) was added dropwise, and the reaction mixture was stirred with a magnetic stirring bar and heated to 50℃in an oil bath for 2 hours to give a yellow solution, and after evaporation of the solvent at 50℃a yellow optically crosslinked polymer gel 1-1 was obtained, see FIGS. 1,2 and 3 for the preparation.
Comparative example 1
2-sulfo-2 '-hydroxy-4, 4' -diformylazobenzene (22.65 mg,0.075 mmol) and 2, 5-dimethoxy terephthalaldehyde (16.67 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 The siloxane polymer (1.00 g) was then added dropwise and the reaction mixture was stirred with a magnetic stirring bar and heated to 60 ℃ in an oil bath for 2h to give a yellow solution. After evaporation of the solvent at 50℃orange photo-crosslinked polymer gels 1-2 were obtained, see FIG. 4 for the preparation.
Ultraviolet and circulation experiments
Referring to FIGS. 5, 6 and 7, after irradiation with 254nm ultraviolet light for different time, the ultraviolet spectrum of organogel 1-1 at 200-900nm was measured, and the cycling experiment was to measure absorbance value of organogel 1-1 at 600nm under alternating irradiation of ultraviolet light and visible light. The ultraviolet spectrogram shows that the gel can change from open-loop to closed-loop structure in 10s under 254nm ultraviolet irradiation, the color is changed from light yellow to dark blue, and the color of the gel can be recovered after visible light irradiation, so that the gel has good photochromic performance, and the reversible cycling spectrogram shows that the gel can repeat the photochromic process at least five times, the absorbance loss is within 5%, and the gel has good reversible cycling performance.
After 328nm ultraviolet light irradiates for different time, ultraviolet spectrograms of the organic gel 1-2 at 200-900nm are measured, the cyclic experiment is to measure absorbance values of the organic gel 1-2 at 478nm under the alternate irradiation of ultraviolet light and visible light, the ultraviolet spectrograms show that the gel can change from cis-form to trans-form in structure for 30s under the irradiation of 328nm ultraviolet light, the color of the gel is changed from orange to brown, and meanwhile, the color of the gel can be recovered after the irradiation of visible light. The photochromic process was repeated five times with an absorbance loss of 15%
Fluorescence experiment
Gel 1-1 in the open-loop state is irradiated with 365nm ultraviolet light to exhibit strong blue fluorescence, and gel 1-1 in the closed-loop state is irradiated with 365nm ultraviolet light to exhibit weak blue fluorescence.
Gel 1-2 in cis and trans state was irradiated with 365nm uv light, and exhibited weak blue fluorescence.
Example 2
1, 2-bis (5-formyl-2-methylthiophene-3-yl) perfluorocyclopentene (31.8 mg,0.075 mmol) and 2, 5-diethoxy terephthalaldehyde (18.75 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 Subsequently, the siloxane polymer (1.00 g) was added dropwise, and the reaction mixture was stirred with a magnetic stirring bar and heated to 50℃in an oil bath for 2 hours to give a yellow solution, and after evaporating the solvent at 50℃a yellow optically crosslinked polymer gel 2-1 was obtained.
Comparative example 2
2-sulfo-2 '-hydroxy-4, 4' -diformylazobenzene (22.65 mg,0.075 mmol) and 2, 5-diethoxy terephthalaldehyde (18.75 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 Subsequently, the siloxane polymer (1.00 g) was added dropwise and the reaction mixture was stirred with a magnetic stirring bar and in an oil bathHeating to 60 ℃ for 2 hours to obtain yellow solution, and evaporating the solvent at 50 ℃ to obtain orange optical cross-linked polymer gel 2-2.
Ultraviolet and circulation experiments
After 254nm ultraviolet light irradiates for different time, ultraviolet spectrograms of the organic gel 2-1 at 200-900nm are measured, a circulation experiment is to measure absorbance values of the organic gel 2-1 at 600nm under alternating irradiation of ultraviolet light and visible light, the ultraviolet spectrograms show that the gel can undergo structural change from open ring to closed ring for 10s under the irradiation of 254nm ultraviolet light, the color of the gel is changed from light yellow to deep blue, meanwhile, after the irradiation of visible light, the color of the gel can be recovered, the gel has good photochromic performance, a reversible circulation spectrogram shows that an organic cage can repeat the photochromic process for at least five times, the absorbance loss is within 5%, and the reversible circulation performance is good.
After different times of 328nm ultraviolet light illumination, determining ultraviolet spectrograms of the organogel 2-2 at 200-900nm, and a cycle experiment is to determine absorbance values of the organogel 2-2 at 478nm under the alternate illumination of ultraviolet light and visible light, wherein the ultraviolet spectrograms show that the gel can change from cis-form to trans-form in structure for 30s under the 328nm ultraviolet light illumination, the color of the gel is changed from orange to brown, meanwhile, the color of the gel can be recovered after the visible light illumination, the photochromic process is repeated for five times, and the absorbance loss is 17%.
Fluorescence experiment
Gel 2-1 in the open-loop state was irradiated with 365nm ultraviolet light, exhibiting strong blue fluorescence. Gel 2-1 in the closed-loop state was irradiated with 365nm ultraviolet light, exhibiting weak blue fluorescence.
Gel 2-2 in both cis and trans state was irradiated with 365nm uv light and exhibited weak blue fluorescence.
Example 3
1, 2-bis (5-formyl-2-methylthiophene-3-yl) perfluorocyclopentene (31.8 mg,0.075 mmol) and 2, 5-dibutoxyterephthalaldehyde (20.85 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 Subsequently, the siloxane polymer (1.00 g) was added dropwise and the reaction mixture was stirred with a magnetic stirring bar and in oilHeating to 50 ℃ in a bath for 2 hours to obtain a yellow solution, and evaporating the solvent at 50 ℃ to obtain the yellow optical cross-linked polymer gel 3-1.
Comparative example 3
2-sulfo-2 '-hydroxy-4, 4' -diformylazobenzene (22.65 mg,0.075 mmol) and 2, 5-dibutoxyterephthalaldehyde (20.85 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 Subsequently, the siloxane polymer (1.00 g) was added dropwise, and the reaction mixture was stirred with a magnetic stirring bar and heated to 60℃in an oil bath for 2 hours to give a yellow solution, and after evaporation of the solvent at 50℃a pale brown optically crosslinked polymer gel 3-2 was obtained.
Ultraviolet and circulation experiments
After 254nm ultraviolet light irradiates for different time, ultraviolet spectrograms of the organic gel 3-1 at 200-900nm are measured, a circulation experiment is to measure absorbance values of the organic gel 3-1 at 600nm under alternating irradiation of ultraviolet light and visible light, the ultraviolet spectrograms show that the gel can undergo structural change from open ring to closed ring for 10s under the irradiation of 254nm ultraviolet light, the color of the gel is changed from light yellow to deep blue, meanwhile, after the irradiation of visible light, the color of the gel can be recovered, the gel has good photochromic performance, a reversible circulation spectrogram shows that an organic cage can repeat the photochromic process for at least five times, the absorbance loss is within 5%, and the reversible circulation performance is good.
After 328nm ultraviolet light irradiates for different time, ultraviolet spectrograms of the organic gel 3-2 at 200-900nm are measured, the cyclic experiment is to measure absorbance value of the organic gel 3-2 at 478nm under the alternate irradiation of ultraviolet light and visible light, the ultraviolet spectrograms show that the gel can change from cis-form to trans-form in 30s under the irradiation of 328nm ultraviolet light, the color is changed from light brown to brown, and meanwhile, the color of the gel can be recovered after the irradiation of visible light. The photochromic process was repeated five times with an absorbance loss of 18%.
Fluorescence experiment
Gel 3-1 in the open-loop state was irradiated with 365nm ultraviolet light, exhibiting strong blue fluorescence. Gel 3-1 in the closed-loop state was irradiated with 365nm ultraviolet light, exhibiting weak blue fluorescence.
Gel 3-2 in cis and trans state was irradiated with 365nm uv light with almost no fluorescence.
Example 4
1, 2-bis (5-formyl-2-methylthiophene-3-yl) perfluorocyclopentene (31.8 mg,0.075 mmol) and 2, 5-dihexyloxy terephthalaldehyde (22.95 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 The siloxane polymer (1.00 g) was then added dropwise and the reaction mixture was stirred with a magnetic stirring bar and heated to 50 ℃ in an oil bath for 2h to give a yellow solution. After evaporation of the solvent at 50℃yellow optically crosslinked polymer gel 4-1 was obtained.
Comparative example 4
2-sulfo-2 '-hydroxy-4, 4' -diformylazobenzene (22.65 mg,0.075 mmol) and 2, 5-dihexyloxy terephthalaldehyde (22.95 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 The siloxane polymer (1.00 g) was then added dropwise and the reaction mixture was stirred with a magnetic stirring bar and heated to 60 ℃ in an oil bath for 2h to give a yellow solution. After evaporation of the solvent at 50℃orange photo-crosslinked polymer gel 4-2 was obtained.
Ultraviolet and circulation experiments
After 254nm ultraviolet light irradiates for different time, ultraviolet spectrograms of the organic gel 4-1 at 200-900nm are measured, a circulation experiment is to measure absorbance values of the organic gel 4-1 at 600nm under alternating irradiation of ultraviolet light and visible light, the ultraviolet spectrograms show that the gel can undergo structural change from open ring to closed ring for 10s under the irradiation of 254nm ultraviolet light, the color of the gel is changed from light yellow to deep blue, meanwhile, after the irradiation of visible light, the color of the gel can be recovered, the gel has good photochromic performance, a reversible circulation spectrogram shows that an organic cage can repeat the photochromic process for at least five times, the absorbance loss is within 5%, and the reversible circulation performance is good.
After 328nm ultraviolet light irradiates for different time, ultraviolet spectrograms of the organic gel 4-2 at 200-900nm are measured, the cyclic experiment is to measure absorbance value of the organic gel 4-2 at 478nm under the alternate irradiation of ultraviolet light and visible light, the ultraviolet spectrograms show that the gel can change from cis-form to trans-form in structure for 30s under the irradiation of 328nm ultraviolet light, the color of the gel is changed from orange to brown, and meanwhile, the color of the gel can be recovered after the irradiation of visible light. The photochromic process was repeated five times with an absorbance loss of 17%.
Fluorescence experiment
Gel 4-1 in the open-loop state was irradiated with 365nm ultraviolet light, exhibiting strong blue fluorescence. Gel 4-1 in the closed-loop state was irradiated with 365nm ultraviolet light, exhibiting weak blue fluorescence.
Gel 4-2 in both cis and trans states was irradiated with 365nm uv light, and exhibited weak blue fluorescence.
Example 5
1, 2-bis (5-formyl-2-methylthiophene-3-yl) perfluorocyclopentene (31.8 mg,0.075 mmol) and 2, 5-bis (octyloxy) terephthalaldehyde (25.05 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 Subsequently, the siloxane polymer (1.00 g) was added dropwise, and the reaction mixture was stirred with a magnetic stirring bar and heated to 50℃in an oil bath for 2 hours to give a yellow solution, and after evaporating the solvent at 50℃a yellow optically crosslinked polymer gel 5-1 was obtained.
Comparative example 4
2-sulfo-2 '-hydroxy-4, 4' -diformylazobenzene (22.65 mg,0.075 mmol) and 2, 5-bis (octyloxy) terephthalaldehyde (25.05 mg,0.075 mmol) were dissolved in 10mL of CHCl in a 100mL round bottom flask 3 The siloxane polymer (1.00 g) was then added dropwise and the reaction mixture was stirred with a magnetic stirring bar and heated to 60 ℃ in an oil bath for 2h to give a yellow solution. After evaporation of the solvent at 50℃orange photo-crosslinked polymer gel 5-2 was obtained.
Ultraviolet and circulation experiments
After 254nm ultraviolet light irradiates for different time, ultraviolet spectrograms of the organic gel 5-1 at 200-900nm are measured, a circulation experiment is to measure absorbance values of the organic gel 5-1 at 600nm under alternating irradiation of ultraviolet light and visible light, the ultraviolet spectrograms show that the gel can undergo structural change from open ring to closed ring for 10s under the irradiation of 254nm ultraviolet light, the color of the gel is changed from light yellow to deep blue, meanwhile, after the irradiation of visible light, the color of the gel can be recovered, the gel has good photochromic performance, a reversible circulation spectrogram shows that an organic cage can repeat the photochromic process for at least five times, the absorbance loss is within 5%, and the reversible circulation performance is good.
After 328nm ultraviolet light irradiates for different time, ultraviolet spectrograms of the organogel 5-2 at 200-900nm are measured, the cyclic experiment is to measure absorbance value of the organogel 5-2 at 478nm under the alternate irradiation of ultraviolet light and visible light, the ultraviolet spectrograms show that the gel can change from cis-form to trans-form in structure for 30s under the irradiation of 328nm ultraviolet light, the color of the gel is changed from orange to brown, and meanwhile, the color of the gel can be recovered after the irradiation of visible light. The photochromic process was repeated five times with an absorbance loss of 17%.
Fluorescence experiment
Gel 5-1 in the open-loop state is irradiated with 365nm ultraviolet light to exhibit strong blue fluorescence, and gel 5-1 in the closed-loop state is irradiated with 365nm ultraviolet light to exhibit weak blue fluorescence.
Gel 5-2 in both cis and trans states was irradiated with 365nm uv light, and exhibited weak blue fluorescence.
The foregoing is a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent variation and variation of the above embodiment according to the technical substance of the present invention falls within the scope of the technical solution of the present invention.

Claims (4)

1. An organogel having photochromism and fluorescence, characterized in that: the organogel has the following structure:
Figure QLYQS_1
R 1 :-CH 3 R 2 :-C 2 H 5 R 3 :-C 4 H 9 R 4 :-C 6 H 13 R 5 :C 8 H 17
r is selected from R 1 、R 2 、R 3 、R 4 、R 5 。
2. A method for preparing an organogel having photochromism and fluorescence as claimed in claim 1, characterized in that: the method for preparing the organogel comprises the following steps:
d1, dissolving the photochromic unit and the luminescent unit in CHCl 3 In (a) and (b);
d2, dropwise adding a siloxane polymer, stirring the reaction mixture by using a magnetic stirring rod, and heating in an oil bath to obtain a yellow solution;
d3, evaporating the solvent to obtain yellow optical crosslinked polymer organogel;
d4, carrying out ultraviolet light illumination detection on the yellow optical crosslinked polymer organic gel, and carrying out structural change from ring opening to ring closing under ultraviolet light illumination, wherein the color is changed from pale yellow to dark blue, and the color of the gel can be recovered after visible light illumination, so that the gel has good photochromic performance;
the light-emitting unit is one of 2, 5-dimethoxy terephthalaldehyde, 2, 5-diethoxy terephthalaldehyde, 2, 5-dibutoxy terephthalaldehyde, 2, 5-dihexyloxy terephthalaldehyde or 2, 5-bis (octyloxy) terephthalaldehyde;
the photochromic unit is a perfluorocyclodiarylethene.
3. A method for preparing an organogel having photochromism and fluorescence as claimed in claim 2, characterized in that: the heating reaction in the step D2 is an imine condensation reaction, provided that the reaction is carried out for 2 hours at 50 ℃.
4. A method for preparing an organogel having photochromism and fluorescence as claimed in claim 2, characterized in that: the D4 step is subjected to structural change from open loop to closed loop under 254nm ultraviolet irradiation.
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AU2002952454A0 (en) * 2002-11-04 2002-11-21 Polymers Australia Pty Limited Photochromic compositions and light transmissible particles
TWI648345B (en) * 2013-12-16 2019-01-21 道康寧公司 Optical material that selectively blocks light and optical devices including such selective light-shielding photophysical materials
CN113234238B (en) * 2021-04-14 2023-07-18 湖北吉人水性汽车涂料有限公司 Light-responsive self-repairing polymer gel and preparation method thereof

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