CN110423426B - Photoresponse composite material, and preparation method and application thereof - Google Patents

Photoresponse composite material, and preparation method and application thereof Download PDF

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CN110423426B
CN110423426B CN201910646459.1A CN201910646459A CN110423426B CN 110423426 B CN110423426 B CN 110423426B CN 201910646459 A CN201910646459 A CN 201910646459A CN 110423426 B CN110423426 B CN 110423426B
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彭海炎
王艺璇
解孝林
周兴平
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Huazhong University of Science and Technology
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Abstract

The invention belongs to the technical field of composite materials, and particularly relates to a photoresponse composite material, and a preparation method and application thereof. Comprising a polymer substrate and dispersed therein carbonized polymer quantum dots, and a photoacid generator or photobase generator; wherein the carbonized polymer quantum dots are capable of emitting fluorescence; the acid generated by the photoacid generator or the organic base generated by the photobase generator can react with the fluorescent light-emitting site of the carbonized polymer quantum dot to quench the fluorescence of the carbonized polymer quantum dot. The photoresponse composite material can regulate and control the fluorescence intensity of different areas by exposing the different areas in a partition mode in the ultraviolet light exposure process, so that information recording is realized; the recorded information has certain stability under sunlight; but information destruction can be achieved by global exposure. The photoresponse composite material has good biocompatibility and low environmental toxicity, and can be used as an anti-counterfeiting label.

Description

Photoresponse composite material, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a photoresponse composite material, and a preparation method and application thereof.
Background
The composite material with controllable fluorescence life can complete an accurate light-controlled fluorescence response process, realize the required patterned storage and information display under special conditions, namely ultraviolet lamp irradiation, and realize the selective destruction of fluorescence patterns, and has important application in the aspects of shelf life detection, high-end anti-counterfeiting, information transmission and destruction of acquired information of food and medicine.
The pattern hiding technology based on fluorescent substances is an important high-end anti-counterfeiting technology. However, the conventional fluorescent substance contains heavy metal atoms, has poor biocompatibility, and is liable to cause light flicker. The carbonized polymer quantum dot is a novel fluorescent material, has higher fluorescence emission quantum efficiency, and has non-flashing fluorescence and excellent light stability compared with the traditional organic or inorganic fluorescein. For example: the fluorescence intensity of the carbonized polymer quantum dots is almost kept unchanged by using a xenon lamp for continuous excitation for several hours, and the organic fluorophore can be photobleached within several minutes. In addition, the self-absorption effect of the carbonized polymer quantum dots is weak, the energy loss is small, and long-time real-time imaging is facilitated. At present, the application of the carbonized polymer quantum dots in the anti-counterfeiting field is mainly to prepare fluorescent ink and print fluorescent patterns. However, the existing carbonized polymer quantum dot printing needs complicated equipment, and the printed information is difficult to erase and is easy to illegally transfer and secondarily use. When the fluorescent display has a long life, the stored information is easily transferred illegally; when the fluorescence display lifetime is short, the pattern easily disappears due to the decay of the fluorescence intensity.
Disclosure of Invention
In response to the above deficiencies or needs in the art, the present invention provides a photoresponsive composite material, its preparation and use, comprising a polymeric matrix material and dispersed therein carbonized polymer quantum dots, and a photoacid generator or photobase generator; the acid generated by the photoacid generator or the organic base generated by the photobase generator can act with the fluorescent luminescent sites of the carbonized polymer quantum dots to attenuate or quench the fluorescence of the carbonized polymer quantum dots, thereby solving the technical problems that the existing carbonized polymer quantum dots are used for preparing fluorescent ink, the equipment for printing fluorescent patterns is complex, and the printed information is difficult to erase.
To achieve the above object, according to one aspect of the present invention, there is provided a photo-responsive composite material comprising a polymer matrix having dispersed therein carbonized polymer quantum dots, and further dispersed therein a photoacid generator or a photobase generator; wherein
The carbonized polymer quantum dots are capable of emitting fluorescence;
the photoacid generator is capable of generating an acid under ultraviolet illumination;
the photobase generator can generate organic base under the irradiation of ultraviolet light;
the acid generated by the photoacid generator or the organic base generated by the photobase generator can interact with the fluorescent light-emitting sites of the carbonized polymer quantum dots to attenuate or quench the fluorescence of the carbonized polymer quantum dots.
Preferably, the composite material comprises 0.01 to 0.05 parts by weight of carbonized polymer quantum dots, 0.1 to 2.5 parts by weight of a photoacid generator, and 97.45 to 99.89 parts by weight of a polymer base material; or
0.01-0.05 weight parts of carbonized polymer quantum dots, 0.1-2.5 weight parts of photobase generating agent and 97.45-99.89 weight parts of polymer base material.
Preferably, the polymeric substrate is polyvinyl alcohol, poly N, N-dimethylacrylamide, polyvinylpyrrolidone, or polyethylene glycol;
the photoacid generator is diphenyl iodonium hexafluorophosphate and/or 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine;
the photobase generator is TBD-HBPh4；
The carbonized polymer quantum dot has a structural formula shown as a formula (I) or a formula (II):
Figure BDA0002133588100000031
preferably, the composite material is in the form of a film.
According to another aspect of the present invention, there is provided a method for preparing the photo-responsive composite material, comprising the steps of:
(1) respectively dissolving a polymer base material, carbonized polymer quantum dots and a photoacid generator in a solvent, and uniformly mixing to obtain a raw material mixed solution; or respectively dissolving the polymer base material, the carbonized polymer quantum dots and the photobase generating agent in a solvent, and uniformly mixing to obtain a raw material mixed solution;
(2) and (2) under a dark condition, placing the raw material mixed liquor obtained in the step (1) in a mould, and removing the solvent to obtain the photoresponse composite material, wherein the composite material comprises a polymer base material, and carbonized polymer quantum dots and a photoacid generator or a photobase generator are dispersed in the polymer base material.
According to another aspect of the present invention, there is provided a use of the light responsive composite material as a light responsive composite material with controllable fluorescence intensity.
Preferably, the composite material is a film, when the film composite material is placed under a mask plate for ultraviolet illumination, the fluorescence of the composite material at the position irradiated by the ultraviolet is attenuated or quenched, and a fluorescence pattern corresponding to the mask plate is displayed after the mask plate is removed; when the composite material showing the fluorescent pattern is further subjected to complete ultraviolet irradiation, the overall fluorescence of the composite material is attenuated or quenched.
Preferably, the ultraviolet light wavelength is 254 nm-365 nm.
Preferably, the mask is a photomask, a real object mask or an electronic mask.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
according to the invention, the carbonized polymer quantum dots, the photoacid generator or the photobase generator and the aqueous polymer matrix are compounded to prepare the composite material, the anti-counterfeiting pattern is formed through subarea exposure, and the life regulation of the fluorescent information of the anti-counterfeiting film can be realized through a mode of destroying the pattern information through integral exposure, so that the requirements on the destruction and protection of the related acquired information are met, but no relevant report is found. The preparation of the controllable photoresponse composite material has the following technical problems: 1. the problem of uniform dispersion of the carbonized polymer quantum dots and the photoacid generator or the photobase generator in the hydrophilic polymer matrix adopted by the composite material; 2. the mass ratio of the carbonized polymer quantum dots and the photoacid generator or the photobase generator in the hydrophilic polymer matrix adopted by the composite material, and the selection of the irradiation wavelength and the intensity of the ultraviolet light source ensure the high contrast of the fluorescent pattern.
The invention provides a photoresponse composite material which comprises a polymer base material, carbonized polymer quantum dots dispersed in the polymer base material, and a photoacid generator or a photobase generator. The invention utilizes the interaction force (mainly hydrogen bond force) between the carbonized polymer quantum dots and the hydrophilic polymer substrate to limit the rotation vibration of the functional groups on the molecular surface of the carbonized polymer quantum dots and weaken the non-radiative transition, thereby realizing and enhancing the fluorescence emission of the composite material and achieving the uniform and stable dispersion of the carbonized polymer quantum dots in the polymer film.
The invention utilizes a simple solvothermal synthesis method to prepare the carbonized polymer quantum dots, the photoacid generator or the photobase generator are added into a water solvent, the mixed solution is placed at normal temperature for uniform dissolution, and the aqueous solution of the hydrophilic polymer is added into the mixed solution, so that the carbonized polymer quantum dots, the photoacid generator or the photobase generator are uniformly dispersed in the hydrophilic polymer base material to form a film. After film formation, the accuracy of the zonal exposure reaction under the assistance of a photomask plate can be ensured, the fluorescence attenuation or quenching of an exposure area is achieved while the fluorescence emission intensity of an unexposed area is kept, and the resolution of a fluorescence pattern formed by the photoresponse composite material is effectively ensured. After the fluorescent pattern is obtained, the overall exposure can realize the overall fluorescence attenuation or quenching of the composite material, and the formed fluorescent pattern is destroyed. The composite material with the photoresponse anti-counterfeiting characteristic has remarkable advantages in the aspects of shelf life detection, high-end anti-counterfeiting, information transmission and destruction of acquired information of food and medicine.
According to the invention, the mass ratio of the carbonized polymer quantum dots and the photoacid generator or the photobase generator in the hydrophilic polymer matrix adopted by the composite material is regulated, and the proper ultraviolet light source irradiation wavelength and intensity selection are selected to ensure the high contrast of the fluorescent pattern.
The anti-counterfeiting film provided by the invention does not need ink and paper, is simple to prepare, convenient to use and environment-friendly, and solves the problems of complex production process, environmental pollution and the like of the traditional printing anti-counterfeiting material; the stored information can be encrypted in a patterned mode, can be read through an electronic terminal, and is suitable for the fields of packaging, anti-counterfeiting and safety.
Drawings
FIG. 1 is a schematic diagram of the preparation and application processes of the anti-counterfeiting composite material film in example 1; wherein FIG. 1A is a photo-responsive composite made in accordance with the present invention; FIG. 1B is a patterned film for storing information after UV illumination; FIG. 1C is the composite material after the overall ultraviolet illumination has been destroyed with the fluorescent pattern destroyed;
FIG. 2 is a fluorescent photograph of the photoresponsive composite of example 1 viewed under a 365nm hand-held ultraviolet lamp before photoresponse occurs;
FIG. 3 is a graph showing the fluorescent pattern of the photoresponsive composite material of example 1 after photoresponse under a 365nm portable ultraviolet lamp;
FIG. 4 is the pattern of a composite film with the stored fluorescence pattern information destroyed after full light exposure of the fluorescence pattern prepared from example 1, seen under a 365nm hand-held ultraviolet lamp.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a photoresponse composite material, which comprises a polymer base material, wherein carbonized polymer quantum dots and a photoacid generator or a photobase generator are dispersed in the polymer base material; wherein
The carbonized polymer quantum dots are capable of emitting fluorescence;
the photoacid generator is capable of generating an acid under ultraviolet illumination;
the photobase generator can generate organic base under the irradiation of ultraviolet light;
the acid generated by the photoacid generator or the organic base generated by the photobase generator can interact with the fluorescent light-emitting sites of the carbonized polymer quantum dots to attenuate or quench the fluorescence of the carbonized polymer quantum dots.
In some embodiments, the composite material comprises 0.01 to 0.05 parts by weight of the carbonized polymer quantum dots, 0.1 to 2.5 parts by weight of the photoacid generator, and 97.45 to 99.89 parts by weight of the polymeric matrix material; or
0.01-0.05 weight parts of carbonized polymer quantum dots, 0.1-2.5 weight parts of photobase generating agent and 97.45-99.89 weight parts of polymer base material.
In some embodiments, the material of the polymeric substrate is one or more of polyvinyl alcohol, poly N, N-dimethylacrylamide, polyvinylpyrrolidone, and polyethylene glycol;
the photoacid generator is diphenyl iodonium hexafluorophosphate and/or 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine; the photoacid generator can be obtained commercially. Wherein the structural formulas of the diphenyl iodonium hexafluorophosphate and the 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine are respectively shown as a formula (three) and a formula (four):
Figure BDA0002133588100000061
the photobase generator is TBD-HBPh4(ii) a The structural formula is shown as the formula (V):
Figure BDA0002133588100000062
Figure BDA0002133588100000071
in some embodiments, the photobase generator TBD-HBPh4The preparation method comprises the following steps:
the base TBD was first dissolved in aqueous hydrochloric acid and a slight excess of NaBPh was added4An aqueous solution. Filtering the salt precipitate, washing with water for several times, washing with ethanol, recrystallizing with mixture of ethanol and chloroform, and vacuum drying to obtain colorless cubic crystal.
The carbonized polymer quantum dot has a structural formula shown as a formula (I) or a formula (II):
Figure BDA0002133588100000072
the carbonized polymer quantum dot can be prepared from an organic precursor with amino or carboxyl through a solvothermal reaction, and the carbonized polymer quantum dot which has different conjugated domains and sizes and emits different fluorescent colors and is shown as a formula (I) or a formula (II) can be obtained by selecting different precursors. When different quantum dot precursors are adopted, the obtained carbonized polymer quantum dot shown in the formula (I) or the formula (II) can display red, green or blue light under the irradiation of ultraviolet light.
In some embodiments, the carbonized polymer quantum dots of the present invention may be prepared as follows:
(1) dissolving a carbonized polymer quantum dot organic precursor in an organic solvent, and stirring to obtain a quantum dot precursor mixed solution;
(2) carrying out solvent thermal reaction on the mixed solution at the temperature of 180-200 ℃ for 300-720 min; cooling and purifying to obtain the carbonized polymer quantum dot solid powder.
In some embodiments, the carbonized polymer quantum dot organic precursor is o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, a mixture of citric acid and ethylene diamine, a mixture of citric acid and 2, 3-diaminonaphthalene, a mixture of citric acid and 1, 5-diaminonaphthalene and sulfuric acid, or a mixture of citric acid and o-phenylenediamine. When the adopted quantum dot organic precursor is o-phenylenediamine, m-phenylenediamine or p-phenylenediamine, correspondingly, the carbonized polymer quantum dot shown in the structural formula (I) is prepared according to the method; when the adopted quantum dot organic precursor is a mixture of citric acid and ethylenediamine, a mixture of citric acid and 2, 3-diaminonaphthalene, a mixture of citric acid and 1, 5-diaminonaphthalene and sulfuric acid or a mixture of citric acid and o-phenylenediamine, the carbonized polymer quantum dot shown in the structural formula (II) is correspondingly prepared according to the method.
In some embodiments, the polymer substrate is a hydrophilic polymer substrate, which is dissolved in water to prepare a solution, and the following method can be used: mixing the polymer base material with deionized water, and stirring to dissolve under heating to obtain an aqueous solution. Generally, a homogeneous phase is required to be formed in preparation of the photoresponse composite material film, and in order to realize uniform dispersion of the photoresponse composite material film in a composite system, an ideal dispersion effect can be achieved by utilizing the hydrogen bonding effect formed by hydrophilic groups on the surface of a hydrophilic polymer substrate and groups on the surface of quantum dots in consideration of the types of the groups on the surface of the carbonized polymer quantum dots.
In some embodiments, the composite material is in the form of a film.
The invention also provides a preparation method of the photoresponse composite material, which comprises the following steps:
(1) respectively dissolving a polymer base material, carbonized polymer quantum dots and a photoacid generator in a solvent, and uniformly mixing to obtain a raw material mixed solution; or respectively dissolving the polymer base material, the carbonized polymer quantum dots and the photobase generating agent in a solvent, and uniformly mixing to obtain a raw material mixed solution;
(2) and (2) under a dark condition, placing the raw material mixed liquor obtained in the step (1) in a mould, and removing the solvent to obtain the photoresponse composite material, wherein the composite material comprises a polymer base material, and carbonized polymer quantum dots and a photoacid generator or a photobase generator are dispersed in the polymer base material.
In some embodiments, the polymer substrate is dissolved in the aqueous solvent in step (1), and the polymer substrate is mixed with water under a shading condition, and then dissolved under heating to obtain an aqueous solution of the polymer substrate; the solvent of the carbonized polymer quantum dots, the photoacid generator or the photobase generator is one or more of water, methanol and dichloromethane.
In some embodiments, the mass ratio of the carbonized polymer quantum dots, the photoacid generator, and the polymer base material in the raw material mixture of step (1) is 0.01 to 0.05: 0.1-2.5: 97.45-99.89; or
The mass ratio of the carbonized polymer quantum dots to the photobase generating agent to the polymer base material is 0.01-0.05: 0.1-2.5: 97.45-99.89.
In some embodiments, in the step (2), the raw material mixture is placed in a groove of a mold, and the photoresponse composite material film can be obtained after the solvent is volatilized. The thickness of the film can be adjusted according to the actual application requirements.
The invention also provides application of the photoresponse composite material, which is used as the photoresponse composite material with controllable fluorescence intensity.
In some embodiments, when the composite material is applied, the composite material is a film, when the film composite material is placed under a mask plate for ultraviolet irradiation, the fluorescence of the composite material at the irradiated position is attenuated or quenched, and a fluorescence pattern corresponding to the mask plate is displayed after the mask plate is removed; when the composite material showing the fluorescent pattern is further subjected to complete ultraviolet irradiation, the overall fluorescence of the composite material is attenuated or quenched.
In some embodiments, the ultraviolet light has a wavelength of 254nm to 365 nm.
In some embodiments, the mask is a photomask, a physical mask or an electronic mask, and the photoresponsive composite material can effectively control the fluorescence response region by adjusting the exposure region, so as to form a desired fluorescence pattern.
The invention provides a photoresponse composite material for forming a fluorescence image visible to naked eyes under an ultraviolet lamp by ultraviolet illumination, and a preparation method and application thereof. When the composite material is applied, the stored information in the composite material is erased through photoresponse, preferably ultraviolet light with the wavelength of 254-365 nm, and the exposure area covers the whole area of the composite material.
The carbonized polymer quantum dots can absorb visible light and transfer energy to a photoacid generator or a photobase generator which can only absorb ultraviolet light, so that quenching response of the composite material under sunlight is further realized. The proportion of the added carbonized polymer quantum dots and the photoacid generator or the photobase generator is different, namely the proportion of the luminescent groups and the quencher is different, the quenching speed has certain difference, and the composite material which is exposed and stored with images by virtue of the photomask is placed under the sunlight, so that the disappearance speed of the images has corresponding difference. The photoresponse of the photoresponse composite material comprises the steps of storing information after the auxiliary subarea exposure of the photomask and displaying a fluorescent pattern, integrally exposing and destroying the fluorescent pattern in time and regulating and controlling a proper proportion to realize different-period limit sunlight responsiveness of fluorescence intensity, and can be used for quality guarantee period detection of food and drugs, controllable life fluorescence anti-counterfeiting and information transmission and protection of acquired information.
The following are examples:
example 1
A photoresponsive composite material capable of forming and displaying patterns and destroying patterns comprises 0.01 wt% of carbonized polymer quantum dots emitting green fluorescence, 0.1 wt% of diphenyl iodonium hexafluorophosphate and 99.89 wt% of polyvinyl alcohol serving as a carrier, wherein the carbonized polymer quantum dots are prepared into an aqueous solution. The composite material with the photoresponse pattern can assist in forming a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the stored fluorescent pattern can be seen under an ultraviolet lamp, and the fluorescence of the whole composite material film can be seen after the composite material film is integrally exposed, namely the stored fluorescent pattern is destroyed.
The photoresponsive composite material was prepared as follows: fully dissolving 0.01 wt% of green carbonized polymer quantum dots and 0.1 wt% of diphenyl iodonium hexafluorophosphate in a proper amount of water, and performing ultrasonic-assisted dispersion at normal temperature to obtain a uniform solution; after the uniform dispersion liquid is cooled to room temperature, adding a proper amount of 99.89 wt% polyvinyl alcohol to prepare an aqueous solution, uniformly mixing, dropwise adding the aqueous solution into a polytetrafluoroethylene groove, and completely volatilizing solvent water to form a film to obtain the photoresponse composite material, as shown in figure 1A. The photo of the composite film actually obtained is shown in FIG. 2.
The green fluorescent carbonized polymer quantum dot is prepared by taking ortho-phenylenediamine as a precursor, and the preparation method comprises the following steps:
a) adding 3g of ortho-phenylenediamine solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution A;
b) transferring the solution A into a plurality of reaction kettles with tetrafluoroethylene liners and 100m L, reacting for 720min at the temperature of 180 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) and obtaining the carbonized polymer quantum dots with green fluorescence.
Storing information in the fluorescent film through a photomask plate, and using a real mask with a recording wavelength of 254nm and a light intensity of 10mW/cm2The irradiation time was 60 seconds, the portion irradiated with light directionally quenched the fluorescence of the fluorescent substance chromophore due to the generation of hydrogen ions by the photoacid generator diphenyliodonium hexafluorophosphate, and the portion not irradiated with light still exhibited fluorescence, and the patterned film storing information was as shown in fig. 1B. The photograph of the composite film actually obtained is shown in FIG. 3.
Then, the light intensity is 10mW/cm at a wavelength of 254nm2The composite material is subjected to maskless light irradiation for 60 seconds, all fluorescence sites of the carbonized polymer quantum dots are completely reacted to generate a fluorescence quenching phenomenon, and a fluorescence pattern formed by the composite material is destroyed, so that the composite material is obtained as shown in fig. 1C. A photograph of the actual resulting unpatterned composite material is shown in figure 4.
Example 2
A photoresponsive composite material capable of forming and displaying patterns and destroying patterns comprises 0.02 weight percent of red carbonized polymer quantum dots, 0.2 weight percent of 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and 99.78 weight percent of poly N, N-dimethylacrylamide serving as a carrier to prepare an aqueous solution. The photoresponse composite material records a fluorescent pattern which is the same as that of the template under ultraviolet exposure, and can see the recorded fluorescent pattern under an ultraviolet lamp, and meanwhile, the fluorescence of the whole film is destroyed after the whole exposure.
The composite material with the light response function is prepared as follows: fully dissolving 0.02 wt% of red carbonized polymer quantum dots in a proper amount of water, adding 0.2 wt% of a uniform solution obtained by dissolving 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine in a mixed solvent of water, methanol and dichloromethane, uniformly mixing the uniform solution with a carbonized polymer quantum dot aqueous solution, and performing ultrasonic-assisted dispersion at normal temperature to obtain a uniform solution; after the uniform dispersion liquid is cooled to room temperature, adding 99.78 wt% of poly N, N-dimethylacrylamide aqueous solution into the uniform dispersion liquid, uniformly mixing, dripping into a groove of a mold, and volatilizing the solvent completely to form a film to obtain the photoresponse composite material, as shown in figure 1A.
The red fluorescent carbonized polymer quantum dot is prepared by taking p-phenylenediamine as a precursor, and the preparation method comprises the following steps:
a) adding 3g of p-phenylenediamine solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution A;
b) transferring the solution A into a plurality of reaction kettles with tetrafluoroethylene liners and 100m L, reacting for 720min at the temperature of 180 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) and obtaining the carbonized polymer quantum dots with red fluorescence.
Storing the information in the composite material without information through a photomask plate, and using a real object mask, wherein the recording wavelength of the photomask is 254 nanometers, and the light intensity is 20mW/cm2The light irradiation time is 20 seconds, and the part irradiated by the light is due to lightThe acid generator 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine generates hydrogen ions to directionally quench the fluorescence of the chromophore of the fluorescent substance, and the part which is not illuminated still has fluorescence, and the patterned composite material with the stored information is shown as figure 1B.
Then, the light intensity is 20mW/cm at a wavelength of 254nm2The whole composite material is subjected to maskless light irradiation for 20 seconds, all fluorescence sites of the carbonized polymer quantum dots are completely reacted to generate a fluorescence quenching phenomenon, pattern information recorded by the composite material film is destroyed, and the obtained film is shown in figure 1C.
Example 3
A photoresponsive composite material capable of forming, displaying and destroying patterns comprises 0.03 wt% of blue carbonized polymer quantum dots and 1.0 wt% of TBD-HBPh4And an aqueous solution of 98.97 wt% polyvinylpyrrolidone as a carrier. The photoresponse composite material can assist in forming a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the formed fluorescent pattern can be seen under an ultraviolet lamp, and the integral fluorescence of the composite material can be seen to be destroyed after the integral exposure.
The photoresponsive composite material was prepared as follows: 0.03 wt% of blue carbonized polymer quantum dots are fully dissolved in a proper amount of water, and 1.0 wt% of TBD-HBPh4Dissolving in a mixed solvent of water, methanol and dichloromethane to obtain a uniform solution, and uniformly mixing with the carbonized polymer quantum dot aqueous solution; adding 98.97 wt% of polyvinylpyrrolidone into the solution to prepare an aqueous solution, uniformly mixing, dripping the aqueous solution into a groove of a mold, and volatilizing the solvent completely to form a film to obtain the photoresponse composite material.
The preparation method of the blue fluorescent carbonized polymer quantum dot comprises the following steps:
a) adding 3g of m-phenylenediamine solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution A;
b) transferring the solution A into a plurality of reaction kettles with tetrafluoroethylene liners and 100m L, reacting for 720min at the temperature of 180 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) obtaining the carbonized polymer quantum dots with blue fluorescence.
Storing the information in the composite material without information through a photomask plate, and using a real object mask, wherein the recording wavelength of the photomask is 254 nanometers, and the light intensity is 30mW/cm2The light irradiation time is 40 s, and the part irradiated by the light is due to the photobase generator TBD-HBPh4The organic base and the luminescent sites form supermolecular aggregation, so that the fluorescence of the carbonized polymer quantum dots is attenuated, the part which is not illuminated still has fluorescence, and the patterned composite material for storing information is shown in FIG. 1B.
Then, the light intensity is 30mW/cm at a wavelength of 254nm2The whole composite material is subjected to maskless light irradiation for 40 seconds, all fluorescence sites of the carbonized polymer quantum dots are completely reacted to generate a fluorescence attenuation phenomenon, a fluorescence pattern formed by the composite material film is destroyed, and the obtained film is shown in figure 1C.
Example 4
A photoresponsive composite material capable of forming and displaying patterns and destroying patterns comprises 0.04 wt% of blue carbonized polymer quantum dots, 1.5 wt% of diphenyl iodonium hexafluorophosphate and 98.46 wt% of polyethylene glycol serving as a carrier, which are dissolved in a proper amount of water to obtain an aqueous solution. The photoresponse composite material can assist in forming a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the fluorescent pattern can be seen under an ultraviolet lamp, and meanwhile, the overall fluorescence attenuation of the composite material can be seen after the overall exposure.
The photoresponsive composite material was prepared as follows: fully dissolving 0.04 wt% of blue carbonized polymer quantum dots and 1.5 wt% of diphenyl iodonium hexafluorophosphate in a proper amount of water, and mixing at normal temperature to obtain a uniform solution; after the uniform solution is cooled to room temperature, adding an aqueous solution obtained by dissolving 98.46 wt% of polyethylene glycol in a proper amount of water, uniformly mixing, dripping into a groove of a mold, and volatilizing the solvent completely to form a film to obtain the photoresponse composite material.
The blue fluorescent carbonized polymer quantum dot is prepared from citric acid and ethylenediamine serving as precursors, and the preparation method comprises the following steps:
a) adding 2g of citric acid solid powder and 1g of ethylenediamine solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution B;
b) transferring the solution B into a plurality of 100m L reaction kettles with tetrafluoroethylene liners, reacting for 300min at the temperature of 200 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) obtaining the carbonized polymer quantum dots with blue fluorescence.
Storing the information in the fluorescent film without information through a photomask plate, and using a real mask, wherein the recording wavelength of the photomask is 254nm, and the light intensity is 40mW/cm2The irradiation time was 30 seconds, the portion irradiated with light was directed to quench the fluorescence of the chromophore of the fluorescent substance due to the generation of hydrogen ions by the photoacid generator diphenyliodonium hexafluorophosphate, the portion not irradiated with light still had fluorescence, and the patterned composite of the stored information is shown in fig. 1B.
Then, the light intensity is 40mW/cm at a wavelength of 254nm2The light irradiates the whole composite material for 30 seconds without a mask, all the fluorescent sites of the carbonized polymer quantum dots in the whole composite material react to generate a fluorescence quenching phenomenon, the fluorescent pattern formed by the composite material film is destroyed, and the obtained composite material is shown as figure 1C.
Example 5
A functionalized composite material with a photoresponse pattern and a photoresponse destruction pattern comprises an aqueous solution prepared from 0.05 wt% of blue carbonized polymer quantum dots, 2.0 wt% of diphenyl iodonium hexafluorophosphate and 97.95 wt% of polymethyl methacrylate as a carrier. The photoresponse composite material can assist in forming a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the fluorescent pattern can be seen under an ultraviolet lamp, and the fluorescence of the whole film can be seen to be destroyed after the whole film is exposed.
The photoresponsive composite material was prepared as follows: fully dissolving 0.05 wt% of blue carbonized polymer quantum dots and 2.0 wt% of diphenyl iodonium hexafluorophosphate in a proper amount of water, and performing ultrasonic-assisted dispersion at normal temperature to obtain a uniform solution; after the uniform dispersion liquid is cooled to room temperature, adding aqueous solution prepared by 97.95 wt% of polymethyl methacrylate, uniformly mixing, dripping the aqueous solution into a groove of a mold, and volatilizing solvent water completely to form a film to obtain the photoresponse composite material.
The preparation method of the blue fluorescent carbonized polymer quantum dot comprises the following steps:
a) adding 2g of citric acid solid powder and 1g of 2, 3-diaminonaphthalene solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution B;
b) transferring the solution B into a plurality of reaction kettles with tetrafluoroethylene liners and 100m L, reacting for 240min at the temperature of 200 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) obtaining the carbonized polymer quantum dots with blue fluorescence.
Storing information in the fluorescent film through a photomask plate, and using a real mask with a recording wavelength of 254nm and a light intensity of 50mW/cm2The light irradiation time was 20 seconds, the portion irradiated with light was oriented to quench the fluorescence of the chromophore of the fluorescent substance due to the generation of hydrogen ions by the photoacid generator diphenyliodonium hexafluorophosphate, the portion not irradiated with light was still fluorescent, and the patterned film of the stored information was as shown in FIG. 1B.
Then, the light intensity is 50mW/cm at a wavelength of 254nm2The whole film is subjected to maskless light irradiation for 30 seconds, all fluorescence sites of the carbonized polymer quantum dots are reacted to generate a fluorescence quenching phenomenon, a fluorescence pattern formed by the composite material film is destroyed, and the obtained film is shown in figure 1C.
Example 6
A photoresponsive composite material having both a photoresponsive pattern and a light-controlled destruction pattern comprises 0.05 wt% of green carbonized polymer quantum dots, 2.5 wt% of 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and 97.45 wt% of polyethylene glycol as a carrier. The photoresponse composite material can assist in forming a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the fluorescent pattern can be seen under an ultraviolet lamp, and the fluorescence of the whole film can be seen to be destroyed after the whole film is exposed.
The photoresponsive composite material was prepared as follows: fully dissolving 0.05 wt% of green carbonized polymer quantum dots in a proper amount of water, completely dissolving 2.5 wt% of 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine in a mixed solvent of water, methanol and dichloromethane, and uniformly mixing with an aqueous solution of the carbonized polymer quantum dots; adding water solution prepared by 97.45 wt% of polyethylene glycol, uniformly mixing, dripping the water solution into a groove of a mold, and volatilizing the solvent completely to form a film to obtain the photoresponse composite material.
The green fluorescent carbonized polymer quantum dot is prepared by using citric acid and 2, 3-diaminonaphthalene as precursors, and the preparation method comprises the following steps:
a) adding 2g of citric acid solid powder and 1g of 2, 3-diaminonaphthalene solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution B;
b) transferring the solution B into a plurality of 100m L reaction kettles with tetrafluoroethylene liners, reacting for 540min at the temperature of 200 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) and obtaining the carbonized polymer quantum dots with green fluorescence.
Storing information in the fluorescent film through a photomask plate, and using a real mask with a recording wavelength of 254nm and a light intensity of 60mW/cm2The light irradiation time is 10 seconds, the part irradiated by the light is directionally quenched due to hydrogen ions generated by the 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine as the photoacid generator, and the part not irradiated by the light still existsFluorescence, a patterned composite film of stored information is shown in FIG. 1B.
Then, the light intensity is 60mW/cm at a wavelength of 254nm2The composite material is subjected to maskless light irradiation for 10 seconds, all fluorescence sites of the carbonized polymer quantum dots are reacted to generate a fluorescence quenching phenomenon, a fluorescence pattern formed by a composite material film is destroyed, and the obtained composite material is shown in figure 1C.
Example 7
A functional composite material with a photoresponse pattern and a photoresponse destruction pattern comprises 0.05 wt% of red carbonized polymer quantum dots and 2.5 wt% of TBD-HBPh4And an aqueous solution of 97.45 wt% poly-N, N-dimethylacrylamide as a carrier. The composite material with the photoresponse pattern performance can be assisted to form a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the fluorescent pattern can be seen under an ultraviolet lamp, and meanwhile, the overall fluorescence of the composite material can be seen to be destroyed after the overall exposure.
The photoresponsive composite material was prepared as follows: 0.05 wt% of red carbonized polymer quantum dots are fully dissolved in a proper amount of water, and 2.5 wt% of TBD-HBPh4Completely dissolving the mixture in a mixed solvent of water, methanol and dichloromethane, and uniformly mixing the mixture with a carbonized polymer quantum dot aqueous solution; then adding water solution prepared by 97.45 wt% of poly N, N-dimethylacrylamide, after uniformly mixing, dropwise adding the water solution into a groove of a mold, and obtaining the photoresponse composite material after the solvent is completely volatilized to form a film.
The red fluorescent carbonized polymer quantum dot is prepared by using citric acid, 1, 5-diaminonaphthalene and sulfuric acid as precursors, and the preparation method comprises the following steps:
a) adding 2g of citric acid solid powder, 1g of 1, 5-diaminonaphthalene solid powder and 50m of L sulfuric acid into 300m of L methanol solvent under the stirring state, and marking the obtained mixed solution as solution C;
b) transferring the solution C into a plurality of reaction kettles with tetrafluoroethylene liners and 100m L, reacting for 60min at the temperature of 200 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) and obtaining the carbonized polymer quantum dots with red fluorescence.
Storing the information in the composite material without information through a photomask plate, and using a real object mask, wherein the recording wavelength of the photomask is 365 nanometers, and the light intensity is 60mW/cm2The light irradiation time is 10 s, and the part irradiated by light is due to the photobase generator TBD-HBPh4The patterned composite material for storing information is shown in FIG. 1B, which generates organic base to form supermolecular aggregation with luminescent site to quench the fluorescence of chromophore of fluorescent substance, and the un-illuminated part still has fluorescence.
Then, the wavelength is 365 nanometers, and the light intensity is 60mW/cm2The composite material is subjected to maskless light irradiation for 10 seconds, all fluorescence sites of the carbonized polymer quantum dots are completely reacted to generate a fluorescence quenching phenomenon, pattern information formed by a composite material film is destroyed, and the obtained composite material is shown in figure 1C.
Example 8
A photoresponsive composite material having both a photoresponsive pattern and a light-controlled destruction pattern comprises 0.05 wt% of blue carbonized polymer quantum dots, 2.5 wt% of diphenyliodonium hexafluorophosphate and 97.45 wt% of polymethacrylate as a carrier in an aqueous solution. The photoresponse composite material can assist in forming a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the fluorescent pattern can be seen under an ultraviolet lamp, and the fluorescence of the whole film can be seen to be destroyed after the whole film is exposed.
The photoresponsive composite material was prepared as follows: fully dissolving 0.05 wt% of blue carbonized polymer quantum dots and 2.5 wt% of diphenyl iodonium hexafluorophosphate in a proper amount of water, and mixing at normal temperature to obtain a uniform solution; after the uniform solution is cooled to room temperature, adding aqueous solution prepared by 97.45 wt% of polymethyl methacrylate, dripping the aqueous solution into a groove of a mold, and forming a film after the solvent is completely volatilized to obtain the photoresponse composite material.
The carbonized polymer quantum dot with blue fluorescence emission is prepared by using citric acid and o-phenylenediamine as precursors, and the preparation method comprises the following steps:
a) adding 2g of citric acid solid powder and 1g of o-phenylenediamine solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution C;
b) transferring the solution C into a plurality of reaction kettles with tetrafluoroethylene liners and 100m L, reacting for 300min at the temperature of 200 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) obtaining the carbonized polymer quantum dots with blue fluorescence.
Storing the information in the composite material without information through a photomask plate, and using a real mask, wherein the recording wavelength of the photomask is 365 nanometers, and the light intensity is 50mW/cm2The irradiation time was 20 seconds, the fluorescence of the chromophore group was directionally quenched by the hydrogen ion generation of the photoacid generator diphenyliodonium hexafluorophosphate in the irradiated portion, and the fluorescence was still present in the non-irradiated portion, and the patterned composite film storing information was as shown in FIG. 1B.
Then, the wavelength is 365 nanometers, and the light intensity is 50mW/cm2The whole composite material is subjected to maskless light irradiation for 20 seconds, all fluorescence sites of the carbonized polymer quantum dots are reacted to generate fluorescence quenching, and a fluorescence pattern formed by the composite material is destroyed, as shown in fig. 1C.
Example 9
A photoresponsive composite material capable of forming and displaying patterns and destroying patterns comprises 0.05 wt% of blue fluorescent carbonized polymer quantum dots, 2.5 wt% of 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine and 97.45 wt% of polymethyl methacrylate as a carrier. The photoresponse composite material can assist in forming a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the fluorescent pattern can be seen under an ultraviolet lamp, and the overall fluorescence of the composite material is seen to be destroyed after the overall exposure.
The preparation method of the photoresponse composite material comprises the following steps: fully dissolving 0.05 wt% of blue carbonized polymer quantum dots in a proper amount of water, fully dissolving 2.5 wt% of 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine in a mixed solvent of water, methanol and dichloromethane, and uniformly mixing with an aqueous solution of the carbonized polymer quantum dots; adding an aqueous solution prepared from 97.45 wt% of polymethyl methacrylate, uniformly mixing, dripping into a groove of a mold, and volatilizing the solvent completely to form a film to obtain the photoresponse composite material.
The preparation method of the blue fluorescent carbonized polymer quantum dot comprises the following steps:
a) adding 2g of citric acid solid powder and 1g of o-phenylenediamine solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution C;
b) transferring the solution C into a plurality of 100m L reaction kettles with tetrafluoroethylene liners, reacting for 240min at the temperature of 200 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) and obtaining the carbonized polymer quantum dots with blue fluorescence in the solution.
Storing information in the fluorescent film through a photomask plate, and using a real mask with a recording wavelength of 365nm and a light intensity of 30mW/cm2The light irradiation time was 10 seconds, the fluorescence of the chromophore was attenuated by the hydrogen ion generated from the photoacid generator diphenyliodonium hexafluorophosphate in the irradiated portion, and the fluorescence remained in the non-irradiated portion, and the patterned composite film storing information was as shown in FIG. 1B.
Then, the wavelength is 365 nanometers, and the light intensity is 30mW/cm2The whole film is subjected to maskless light irradiation for 10 seconds, all fluorescence sites of the carbonized polymer quantum dots are reacted to generate a fluorescence quenching phenomenon, the pattern information formed by the composite material is destroyed, and the obtained film is shown in figure 1C.
Example 10
A photoresponsive composite material capable of forming and displaying patterns and destruction patterns comprising 0.05% by weight of blue fluorescent carbonising polymer quantum dots, 2.5% by weight of diphenyliodonium hexafluorophosphate and 97.45% by weight of polyvinyl alcohol as a carrier in aqueous solution. The photoresponse composite material can assist in forming a fluorescent pattern which is the same as that of the template under ultraviolet exposure through the photomask plate, the fluorescent pattern can be seen under an ultraviolet lamp, and the overall fluorescence of the composite material is seen to be destroyed after the overall exposure.
The photoresponsive composite material was prepared as follows: fully dissolving 0.05 wt% of blue carbonized polymer quantum dots and 2.5 wt% of diphenyl iodonium hexafluorophosphate in a proper amount of water, and mixing at normal temperature to obtain a uniform solution; after the uniform dispersion liquid is cooled to room temperature, adding an aqueous solution prepared from 97.45 wt% of polyvinyl alcohol, uniformly mixing, dropwise adding into a groove of a mold, and completely volatilizing the solvent to form a film to obtain the photoresponse composite material.
The preparation method of the blue fluorescent carbonized polymer quantum dot comprises the following steps:
a) adding 2g of citric acid solid powder and 1g of o-phenylenediamine solid powder into 300m of L ethanol solvent under the stirring state, and marking the obtained mixed solution as solution C;
b) transferring the solution C into a plurality of reaction kettles with tetrafluoroethylene liners and 100m L, reacting for 480min at 200 ℃, transferring the mixture into a flask after the reaction kettles are cooled, processing to obtain a solid, and purifying the product;
c) the carbonized polymer quantum dots with blue fluorescence characteristics are obtained.
Storing information in the fluorescent film through a photomask plate, and using a real mask with a recording wavelength of 365nm and a light intensity of 10mW/cm2And the irradiation time is 60 seconds, the part irradiated by light directionally quenches the fluorescence of the chromophore of the fluorescent substance due to the generation of hydrogen ions by the diphenyl iodonium hexafluorophosphate serving as the photoacid generator, the part not irradiated by light still has fluorescence, and the patterned composite film storing information is shown as figure 1B.
Then, the wavelength is 365 nanometers, and the light intensity is 10mW/cm2The whole composite material is subjected to maskless light irradiation for 60 seconds, all fluorescence sites of the carbonized polymer quantum dots are completely reacted to generate a fluorescence quenching phenomenon, and the pattern information recorded by the composite material film is destroyed, as shown in fig. 1C.
Comparative example 1
Fully dissolving 0.05 wt% of the green carbonized polymer quantum dots prepared from o-phenylenediamine in water at room temperature, then adding an aqueous solution prepared from 99.95 wt% of polyvinyl alcohol, uniformly dissolving again, dropwise adding the solution into a groove of a mold, and completely volatilizing the solvent to obtain a composite material of the carbonized polymer quantum dots and the polyvinyl alcohol, placing the composite material in a 365nm ultraviolet environment with the assistance of a photomask plate and using 10mW/cm2The light intensity of the composite material is exposed for 60 seconds, and only a whole piece of fluorescent film can be obtained, namely the composite material can observe whole fluorescence under a 365nm ultraviolet lamp, cannot obtain a fluorescent pattern through ultraviolet exposure under the assistance of a photomask plate, and cannot eliminate the fluorescence of the composite material through the whole exposure.
Comparative example 2
Dissolving 0.05 wt% of the blue carbonized polymer quantum dot prepared from citric acid and 2, 3-diaminonaphthalene in water and fully dissolving, then adding an aqueous solution prepared from 99.95 wt% of polymethyl methacrylate into the solution, dissolving uniformly again and dropwise adding the solution into a mold groove, obtaining a carbonized polymer quantum dot and polymethyl methacrylate composite material after the solvent is completely volatilized, placing the composite material in an ultraviolet environment with the wavelength of 40mW/cm under the assistance of a photomask plate2The composite material can only obtain integral fluorescence after being exposed for 10 seconds, namely the composite material can observe the fluorescence under an ultraviolet lamp with 254nm, cannot obtain a fluorescence pattern through ultraviolet exposure under the assistance of a photomask plate, and cannot eliminate the fluorescence of the composite material through the integral exposure.
Comparative example 3
Dissolving 0.05 wt% of the red carbonized polymer quantum dots prepared from citric acid, 1, 5-diaminonaphthalene and sulfuric acid in water, fully dissolving, adding 99.95 wt% of aqueous solution prepared from polyvinylpyrrolidone into the solution, dissolving uniformly again, and dripping into a groove of a mold until the solvent is dissolvedCompletely volatilizing to obtain the composite material of the carbonized polymer quantum dots and the polyvinylpyrrolidone, placing the composite material in a 365nm ultraviolet environment with the assistance of a photomask plate and using 40mW/cm2The composite material still sees the whole fluorescence after being exposed for 10 seconds, namely the composite material can observe the fluorescence under a 365nm ultraviolet lamp, cannot obtain a fluorescence pattern through ultraviolet exposure under the assistance of a photomask plate, and cannot eliminate the fluorescence of the composite material through the whole exposure.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (7)

1. A photoresponse composite material is characterized by comprising a polymer base material, wherein carbonized polymer quantum dots and a photoacid generator or a photobase generator are dispersed in the polymer base material; wherein
The carbonized polymer quantum dots are capable of emitting fluorescence;
the photoacid generator is capable of generating an acid under ultraviolet illumination;
the photobase generator can generate organic base under the irradiation of ultraviolet light;
the acid generated by the photoacid generator or the organic base generated by the photobase generator can react with the fluorescent light-emitting site of the carbonized polymer quantum dot to attenuate or quench the fluorescence of the carbonized polymer quantum dot;
the composite material comprises 0.01-0.05 weight part of carbonized polymer quantum dots, 0.1-2.5 weight parts of photoacid generator and 97.45-99.89 weight parts of polymer base material; or
0.01-0.05 parts by weight of carbonized polymer quantum dots, 0.1-2.5 parts by weight of photobase generator and 97.45-99.89 parts by weight of polymer base material;
the polymer base material is polyvinyl alcohol, poly N, N-dimethylacrylamide, polyvinylpyrrolidone or polyethylene glycol.
2. The photo-responsive composite of claim 1 wherein the photo-acid generator is diphenyliodonium hexafluorophosphate and/or 2- (4-methoxyphenyl) -4, 6-bis (trichloromethyl) -1,3, 5-triazine;
the photobase generator is TBD-HBPh4；
The carbonized polymer quantum dot has a structural formula shown as a formula (I) or a formula (II):
Figure FDA0002496760850000021
3. the light-responsive composite of claim 1, wherein the composite is in the form of a film.
4. A method of preparing a photoresponsive composite material according to any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) respectively dissolving a polymer base material, carbonized polymer quantum dots and a photoacid generator in a solvent, and uniformly mixing to obtain a raw material mixed solution; or respectively dissolving the polymer base material, the carbonized polymer quantum dots and the photobase generating agent in a solvent, and uniformly mixing to obtain a raw material mixed solution;
(2) and (2) under a dark condition, placing the raw material mixed liquor obtained in the step (1) in a mould, and removing the solvent to obtain the photoresponse composite material, wherein the composite material comprises a polymer base material, and carbonized polymer quantum dots and a photoacid generator or a photobase generator are dispersed in the polymer base material.
5. Use of a light responsive composite material according to any of claims 1 to 3 as a light responsive composite material with controllable fluorescence intensity;
the composite material is a film, when the film composite material is placed under a mask plate for ultraviolet illumination, the fluorescence of the composite material at the position irradiated by light is attenuated or quenched, and a fluorescence pattern corresponding to the mask plate is displayed after the mask plate is removed; when the composite material showing the fluorescent pattern is further subjected to complete ultraviolet irradiation, the overall fluorescence of the composite material is attenuated or quenched.
6. The use of claim 5, wherein the ultraviolet light has a wavelength of 254nm to 365 nm.
7. The use according to claim 5, wherein the mask is a photomask, a physical mask or an electronic mask.
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