CN111978452B

CN111978452B - Color-changeable polystyrene cross-linked fluorescent microsphere and preparation method thereof

Info

Publication number: CN111978452B
Application number: CN202010670324.1A
Authority: CN
Inventors: 孙宾
Original assignee: Shanghai Donghua Jingyue Asset Management Co ltd; Donghua University
Current assignee: Shanghai Donghua Jingyue Asset Management Co ltd; Donghua University
Priority date: 2020-07-13
Filing date: 2020-07-13
Publication date: 2022-11-25
Anticipated expiration: 2040-07-13
Also published as: CN111978452A

Abstract

The invention relates to a color-changeable Polystyrene (PS) cross-linked fluorescent microsphere and a preparation method thereof, wherein the preparation method comprises the following steps: (1) Mixing styrene, 1-vinyl-7-Br-perylene bisimide derivative and peroxide initiator to obtain a mixture; (2) Adding the mixture into deionized water and the emulsion under the stirring condition, quickly heating to T, and stopping the reaction after a period of time to obtain emulsion; (3) And adding a demulsifier into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere. The invention adopts emulsion polymerization to successfully prepare the color-changeable PS microspheres with the average diameter of 150-400 nm, the aperture variance of 0.9-1.8 and the specific surface area of 750-800 m ² g ^‑1 The fluorescence quantum yield is 60-80%, the color change is shown along with the infiltration amount of the organic solvent under a certain temperature condition, and the organic solvent is a good solvent of the 1-vinyl-7-Br-perylene bisimide derivative.

Description

Color-changeable polystyrene cross-linked fluorescent microsphere and preparation method thereof

Technical Field

The invention belongs to the technical field of color-changing materials, and relates to a polystyrene cross-linked fluorescent microsphere with variable colors and a preparation method thereof.

Background

The fluorescent microspheres are solid particles which have particle sizes ranging from dozens of nanometers to dozens of micrometers and can emit fluorescence after being radiated by external energy, and the fluorescent microspheres are various in shape and are generally spherical. Such functional materials are generally obtained by loading a fluorescent substance on the surface or inside thereof by a physical or chemical method using organic or inorganic microspheres as a carrier.

At present, common fluorescent microspheres mainly include organic polymer fluorescent microspheres, natural polymer microspheres, inorganic fluorescent microspheres, and the like. The organic polymer microsphere has become an important material for preparing the fluorescent microsphere due to the characteristics of excellent performance, simple preparation method and the like. The fluorescent microspheres are prepared by a very large number of methods, which are different from the operation method in principle, but the most common methods include the following methods: preparing carrier microspheres in advance, and then loading fluorescent substances on the surfaces of the carrier microspheres; or the fluorescent substance and the monomer for synthesizing the microsphere are loaded in the sphere in a copolymerization mode; fluorescent materials can also be directly embedded in the sphere to prepare the fluorescent microsphere in the polymerization process; in addition, there are also a lot of literature reports on self-assembly methods for preparing fluorescent microspheres.

Compared with the micromolecule fluorescent material, the fluorescent microsphere has the advantages of relatively stable morphological structure and luminous behavior, and is less influenced by external conditions such as solvent, heat, electricity, magnetism and the like; compared with a homogeneous phase fluorescence sensor, the fluorescent microsphere overcomes the defects of difficult device formation, incapability of repeated use, easy pollution to a system to be detected and the like; compared with a fluorescent film, the micro-nano-scale microspheres have very large specific surface area, and when the micro-nano-scale microspheres are used as a carrier of a fluorescent sensor, sensing molecules can be more effectively contacted with a component to be detected, so that the sensitivity of the sensor is remarkably improved.

With the continuous development and progress of science and technology, the application of fluorescent microsphere materials in various high-precision technical fields, such as immunoassay technology, biological labeling and tracing, high-throughput drug screening, immobilized enzyme and gene research, chemical and biological detection, optical devices and other high-tech fields, is accompanied by the application of fluorescent microspheres.

The series of excellent performances and wide application prospects make the fluorescent microspheres quickly become a research hotspot direction in the fields of preparation and application of fluorescent materials.

The biological discoloration phenomenon is commonly existing in nature, such as a representative chameleon, which can change the color of the biological chameleon according to the change of the external environment and reduce the biological chameleon in another environment, thereby realizing the camouflage of the color or the storage of the heat of the biological chameleon. Based on the above, the color change phenomenon studied in the current price section of the bionic material mainly includes: electrochromic, photochromic, thermochromic, and the like. And the preparation of the fluorescent color-changing microspheres also has very high application value. The color-changing material can be divided into reversible color-changing material and irreversible color-changing material, the color of the reversible color-changing material changes when the surrounding environment changes, the color recovers when the surrounding environment recovers, and the irreversible color-changing material does not have a recovery function, so the reversible color-changing material is widely applied. The thermoreversible color-changing material is different from the traditional material, can make color reaction to the change stimulus of the environmental temperature, and can provide visual information feedback about the temperature for a user in time. Among a plurality of color-changing materials, the organic reversible thermochromic material has adjustable color-changing temperature, various color combinations, obvious color change and low price, so the organic reversible thermochromic material is the most widely researched and has the strongest practicability.

Patent CN101225296A adopts an in-situ polymerization method to wrap a photochromic compound solution in melamine-formaldehyde resin, so as to prepare a photochromic microcapsule, isolate the photochromic material from the external environment, effectively protect the photochromic material, and realize the permanent solidification of the photochromic material. However, the organic solvents adopted by the organic solvents are benzene, ethanol, toluene, tetrachloroethylene or carbon tetrachloride and the like with low boiling point and strong toxicity, which are easy to cause harm to human bodies or environment and limit the application of the organic solvents to a certain extent. More importantly, the capsule with the single core-shell structure wrapping the liquid capsule core has poor mechanical property and thermal stability, and the application of the capsule in the field of polymer processing is limited.

The preparation method of the composite structure microsphere provided by patent CN102814153B is to use polyelectrolyte as molecular glue, and fix the convergent acetylene vesicles with sensing function on the surface of the polystyrene microsphere to form a composite structure with biosensing detection function.

Patent CN109944073A prepared a solvent-induced color-changing photonic crystal fabric, which preparation includes: dispersing P (St-BA-AA) colloidal microspheres with a core-shell structure in water, uniformly mixing with trace acetylene black by ultrasonic, then uniformly loading the mixture on the surface of the fabric, and drying to obtain the solvent-induced color-changing fabric.

The spiropyran is one of the earliest and most extensive systems studied in organic photochromic materials, has quick and reversible photochromic effect, also has the functions of lyotropic discoloration, electrochromism, mechanochromism, acid-base discoloration and the like, and can be used as an intelligent response material in a plurality of fields such as chemical sensors, optical switches, information storage and the like. However, spiropyrans are susceptible to oxidative degradation from environmental factors, resulting in poor fatigue resistance. The spiropyran is wrapped in the polymer microsphere, so that loss of the micromolecule photochromic material due to migration can be avoided, damage to the photochromic material due to direct contact with external environments such as external oxygen, acid, alkali and the like can be reduced, and the color-changing service life of the photochromic material can be further prolonged. However, the difficulty of the packaging operation and the requirement of the dye are simultaneously met, the color-changing material absorbs the color-changing dye into microspheres through physical adsorption, the dye adsorption fastness is limited, and the color-changing material is easy to decolor. At present, a feasible and effective preparation method of the color-changing fluorescent microsphere which is convenient to produce is rarely reported.

Disclosure of Invention

The invention aims to solve the problems in the prior art and provides a polystyrene cross-linked fluorescent microsphere with variable colors and response to temperature and a solvent and a preparation method thereof.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the invention relates to a color-changeable polystyrene cross-linked fluorescent microsphere, which is a polystyrene microsphere taking a dimer of 1-vinyl-7-Br-perylene imide derivatives as a cross-linking agent (note that the cross-linking agent is a dimer of 1-vinyl-7-Br-perylene imide derivatives, which is particularly indicated to be disconnected in some special cases, such as infiltration of a large amount of organic solvents, when no organic solvent is used for infiltration;

the dimer of the 1-vinyl-7-Br-perylene bisimide derivative is formed by combining two 1-vinyl-7-Br-perylene bisimide derivatives through pi-pi interaction between perylene core structures of the two 1-vinyl-7-Br-perylene bisimide derivatives to form a dimer which has a fixed arrangement structure and two vinyl structures; the pi-pi interaction is a weak interaction and sensitive to environmental changes, and the distance between dimers of the interaction changes along with the environmental changes; conjugated molecules bound by such weak interaction as pi-pi interaction can change the charge arrangement of the molecule, thereby changing its photoelectric properties, such as its color and fluorescence emission; the tighter the binding between conjugated molecules through pi-pi interactions, the more the color of the molecule tends to be in the long wavelength direction (red-shifted);

the 1-vinyl-7-Br-perylene bisimide derivative is perylene bisimide which is provided with a vinyl group at the 1 position and a Br atom substituent at the 7 position in the gulf positions (1, 7 positions) and is connected with a bulky substituent at the imide position, and the substitution of the imide position is to prevent the 1-vinyl-7-Br-perylene bisimide derivative from generating polymer aggregation so that the aggregation state of the derivative stays in a dimer state;

the color of the color-changeable polystyrene cross-linked fluorescent microsphere is changed along with the infiltration amount of an organic solvent under a certain temperature condition, and the organic solvent is a good solvent of the 1-vinyl-7-Br-perylene bisimide derivative, so that the movement capacity of molecules is increased, and the inter-molecular distance is increased.

As a preferred technical scheme:

the color-changeable polystyrene cross-linked fluorescent microsphere can show color change along with the infiltration amount of the organic solvent under a certain temperature condition, and specifically means that:

when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from initial deep red to orange red; wherein the organic solvent is tetrahydrofuran, dichloromethane or toluene; the small amount of organic solvent is that the volume ratio of the color-changeable polystyrene cross-linked fluorescent microspheres to the organic solvent is 1; the solvent amount is small, the temperature is low, the molecular motion capability is weak, the pi-pi interaction between molecules is strong, and the dimer is tightly combined;

or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from the initial deep red to orange yellow when the polystyrene cross-linked fluorescent microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; wherein the organic solvent is tetrahydrofuran, dichloromethane or toluene; the small amount of organic solvent is that the volume ratio of the color-changeable polystyrene cross-linked fluorescent microspheres to the organic solvent is 1; the solvent amount is small, but the temperature is high, the molecular motion capability is enhanced, the pi-pi interaction between molecules is weak, and the dimer is loosely combined;

or, when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere capable of changing color changes from initial deep red to orange yellow; wherein the organic solvent is tetrahydrofuran, dichloromethane or toluene; the volume ratio of the variable-color polystyrene cross-linked fluorescent microspheres to the organic solvent is 1.1-10; the solvent amount is large, the molecular movement capacity is enhanced, the pi-pi interaction among molecules is weaker, and the dimer is loosely combined;

after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the color of the variable-color polystyrene cross-linked fluorescent microsphere is recovered to be deep red, and the mutual recognition of the 1-vinyl-7-Br-perylene imide derivatives is caused by the pi-pi interaction in the solvent removal process, so that the original dimer state is recovered.

The color-changeable polystyrene cross-linked fluorescent microsphere as described above, wherein the color change further comprises a change in fluorescent color which is a change in the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere that changes color under excitation of a wavelength of 440 to 460nm and a change in the fluorescent color of the polystyrene cross-linked fluorescent microsphere that changes color:

the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable at the normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red;

when the polystyrene cross-linked fluorescent microsphere is soaked in a small amount of organic solvent at normal temperature, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is 5-8 nm; the fluorescence color of the microsphere is orange red;

when the polystyrene cross-linked fluorescent microspheres are soaked in a small amount of organic solvent and placed at the temperature of between 40 and 50 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the color-changeable polystyrene cross-linked fluorescent microspheres is between 10 and 15nm; the fluorescence color of the microsphere is orange yellow;

when the polystyrene cross-linked fluorescent microsphere is soaked in a large amount of organic solvent at normal temperature, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is 10-15 nm; the fluorescence color of the microsphere is orange yellow;

after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered to deep red. In the solvent removal process, the mutual recognition of the 1-vinyl-7-Br-perylene bisimide derivatives is caused by the pi-pi interaction, and the original dimer state is recovered.

The color-changeable polystyrene cross-linked fluorescent microsphere is characterized in that the bulky substituent is silsesquioxane or a long alkyl chain with a side chain;

the silsesquioxane is

R is isobutyl or isooctyl;

the long alkyl chain with side chain is

Wherein

Indicates that the linking position of the chemical bond is an N atom in the imide structure.

The color-changeable polystyrene cross-linked fluorescent microsphere has the average diameter of 150-400 nm, the pore diameter variance of 0.9-1.8 and the specific surface area of 750-800 m ² g ^-1 The yield of fluorescence quantum is 60-80%.

The invention also provides a preparation method of the polystyrene cross-linked fluorescent microsphere with variable colors, which comprises the following steps:

(1) Mixing styrene, 1-vinyl-7-Br-perylene bisimide derivative and peroxide initiator to obtain a mixture;

(2) Adding the mixture into deionized water and the emulsion under the stirring condition, quickly heating to T, and stopping the reaction after a period of time to obtain emulsion;

(3) And adding a demulsifier into the emulsion under the stirring condition, filtering after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere.

In the preparation method of the color-changeable polystyrene cross-linked fluorescent microsphere, the mass ratio of the peroxide initiator to the styrene is 1; the molar ratio of the styrene to the 1-vinyl-7-Br-perylene imide derivative is 5-6; the peroxide initiator is dibenzoyl peroxide (BPO).

The rapid temperature rise is carried out within 5 minutes, the T is 75-90 ℃, and the period of time is 2-6 hours.

The preparation method of the color-changeable polystyrene cross-linked fluorescent microsphere comprises the following steps of (1) preparing an emulsion by mass ratio of 0.5-3.

According to the preparation method of the color-changeable polystyrene cross-linked fluorescent microsphere, the demulsifier is sodium chloride, and the mass ratio of the demulsifier to the styrene is 1.2-8.

The principle of the invention is as follows:

the invention adopts the dimer of the 1-vinyl-7-Br-perylene bisimide derivative as a cross-linking agent in the polystyrene microsphere, the dimer is combined through pi-pi interaction, and each molecule has one ethylene group, and the dimer has two ethylene groups, so that the dimer can become the cross-linking agent of a high molecular network. Dimers formed by pi-pi interaction bonding are sensitive to temperature and solvent as crosslinks in microspheres, and may have a tendency to undergo a transition to a unimolecular state in the presence of their good or higher temperatures. Moreover, the overall color of the system has a clear relationship with the binding state of the molecules therein. The color of the microsphere in a dimer state is deep red, and the color of the microsphere in a monomer state is orange yellow, so that the polystyrene fluorescent microsphere using the dimer of the 1-vinyl-7-Br-perylene bisimide derivative as a cross-linking agent in the polystyrene microsphere has the color change performance sensitive to temperature and solvent. Because the dimers of the 1-vinyl-7-Br-perylene bisimide derivative are linked through non-covalent bond action, the environment responsiveness is realized, the arrangement of the dimers can change along with the change of the environment, the microsphere has the reversible color change performance, the 1-vinyl-7-Br-perylene bisimide derivative is rearranged into the dimer after the organic solvent is removed and the normal temperature is recovered, and the color of the microsphere is recovered to be deep red.

Advantageous effects

(1) The color-changeable polystyrene cross-linked fluorescent microsphere has the advantages of stable chemical property, high fluorescence intensity and the like, and has great application potential in the fields of biological medicine and electronics;

(2) The preparation method of the color-changeable polystyrene crosslinking fluorescent microsphere is simple, the production cost is low, the preparation is easy, and the obtained product has a wide application range.

Drawings

FIG. 1 is a schematic diagram showing the color change of the color-changeable polystyrene cross-linked fluorescent microsphere according to the invention along with the infiltration amount of the organic solvent.

Detailed Description

The present invention will be further described with reference to the following embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.

In the embodiment of the present invention, all the organic solvents are selected from tetrahydrofuran, dichloromethane and toluene, all the small amounts of organic solvents refer to a volume ratio of the color-changeable polystyrene crosslinked fluorescent microspheres to the organic solvents of 1.

Example 1

The preparation method of the 1-vinyl-7-Br-perylene bisimide derivative comprises the following steps:

the imide site bulky substituent access method comprises the following steps:

the crude product PTCDA-Br was charged in a 250mL three-necked flask

(0.50g, 0.91mmol) and 15.00mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25 ℃ for 1h. Followed by the addition of 2-ethylhexylamine

(4.5 mmol), glacial acetic acid (1695l, 140mmol). Heating to 85 ℃ under the protection of nitrogen, and continuing the reaction for 7 hours. After the reaction was completed, it was cooled to room temperature, and then 120.00mL of methanol was added thereto, followed by stirring overnight. And (4) carrying out suction filtration to obtain a red solid, carrying out vacuum drying for 24h, at 85 ℃, and carrying out column chromatography to obtain 1,7-Br-PDI-X.

The bay position double bond substituent access method comprises the following steps:

1,7-Br-PDI-X (77.4mg, 0.10mmol) was placed in a 50mL eggplant-shaped flask, and HPLC-grade THF (20 mL) was added thereto and sufficiently dissolved with stirring, and the mixture was heated at 45 ℃ to give a orange-yellow color. Subsequently, anhydrous potassium carbonate (55.4 mg, 0.40mmol) and 18-crown-6-ether (105.73mg, 0.40mmol) were added to the system, and the mixture was pipetted by a pipette

(0.25 mmol) was added to the system and the system color change was closely noted throughout the reaction and observed once on TLC spot plate at 15min intervals.

The system becomes orange red after 15min, becomes bright red after 30min, becomes dark red after 45min, finally becomes purple red, TLC point plate shows that the raw material point disappears at 1h, and the reaction is stopped after 2 h. After the solvent is dried by spinning, the product is extracted by trichloromethane and water, and anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system are removed by water. The middle lower layer of the separating funnel is an organic phase, the upper layer is a water phase, the organic phase is purple red, and the water phase is pink. And (3) spin-drying the extracted trichloromethane solution to obtain a 1-vinyl-7-Br-perylene bisimide derivative crude product, and performing column chromatography to obtain a product 1-vinyl-7-Br-perylene bisimide derivative.

Example 2

the imide site bulky substituent access method comprises the following steps:

the crude product PTCDA-Br was charged in a 250mL three-necked flask

(0.50g, 0.91mmol) and 1-methyl-2-pyrrolidone (NMP) 15.00mL and the solid dissolved and stirred at 25 ℃ for 1h. Is then added

R is isobutyl (4.5 mmol), glacial acetic acid (1695 ml, 140mmol). The temperature is raised to 85 ℃ under the protection of nitrogen, and the reaction is continued for 7h. After the reaction was completed, it was cooled to room temperature, and then 120.00mL of methanol was added thereto, followed by stirring overnight. And (4) carrying out suction filtration to obtain a red solid, carrying out vacuum drying for 24h, and carrying out column chromatography at 85 ℃ to obtain 1,7-Br-PDI-X.

1,7-Br-PDI-X (77.4 mg,0.10 mmol) was put in a 50mL eggplant-shaped flask, and HPLC grade THF (20 mL) was added thereto and sufficiently dissolved with stirring, and the mixture was heated at 45 ℃ to give a system orange yellow. Subsequently, anhydrous potassium carbonate (55.4 mg, 0.40mmol) and 18-crown-6-ether (105.73mg, 0.40mmol) were added to the system, and the mixture was pipetted by a pipette

(0.25 mmol) was added to the system and the system was closely focused on color change throughout the reaction and observed once on TLC spot plate at 15min intervals.

The system becomes orange red after 15min, becomes bright red after 30min, becomes dark red after 45min, finally becomes purple red, TLC point plate shows that the raw material point disappears at 1h, and the reaction is stopped after 2 h. After the solvent is dried by spinning, the product is extracted by trichloromethane and water, and anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system are removed by water. The lower layer in the separating funnel is an organic phase, the upper layer is a water phase, the organic phase is purple red, and the water phase is pink. And (3) spin-drying the extracted trichloromethane solution to obtain a 1-vinyl-7-Br-perylene bisimide derivative crude product, and performing column chromatography to obtain a product 1-vinyl-7-Br-perylene bisimide derivative.

Example 3

The preparation method of the 1, 7-vinyl-perylene imide derivative comprises the following steps:

the imide site bulky substituent access method comprises the following steps:

the crude product PTCDA-Br was added to a 250mL three-necked flask

(0.50g, 0.91mmol) and 1-methyl-2-pyrrolidone (NMP) 15.00mL and the solid dissolved and stirred at 25 ℃ for 1h. Followed by the addition of 2-ethylhexylamine

1,7-Br-PDI-X (77.4mg, 0.10mmol) was placed in a 50mL eggplant-shaped flask, and HPLC-grade THF (20 mL) was added thereto and sufficiently dissolved with stirring, and the mixture was heated at 45 ℃ to give a orange-yellow color. Anhydrous potassium carbonate (55.4 mg, 0.40mmol) and 18-crown-6-ether (105.73mg, 0.40mmol) were then added to the system and pipetted using a pipette gun

The system becomes orange red after 15min, becomes bright red after 30min, becomes dark red after 45min, finally becomes purple red, TLC point plate shows that the raw material point disappears at 1h, and the reaction is stopped after 2 h. The solvent was dried by spinning, the product was extracted with chloroform and water, and anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol were removed with water. The lower layer in the separating funnel is an organic phase, the upper layer is a water phase, the organic phase is purple red, and the water phase is pink. And spin-drying the extracted trichloromethane solution to obtain a crude product of the 1-vinyl-7-Br-perylene bisimide derivative, and performing column chromatography to obtain a product of the 1-vinyl-7-Br-perylene bisimide derivative.

Example 4

the imide site large-volume substituent access method comprises the following steps:

the crude product PTCDA-Br was charged in a 250mL three-necked flask

(0.50g, 0.91mmol) and 15.00mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25 ℃ for 1h. Then adding,

(4.5 mmol), glacial acetic acid (1695 mL, 140mmol). Heating to 85 ℃ under the protection of nitrogen, and continuing the reaction for 7 hours. After the reaction was completed, it was cooled to room temperature, and then 120.00mL of methanol was added thereto, followed by stirring overnight. And (4) carrying out suction filtration to obtain a red solid, carrying out vacuum drying for 24h, and carrying out column chromatography at 85 ℃ to obtain 1,7-Br-PDI-X.

The system becomes orange red after 15min, becomes bright red after 30min, becomes dark red after 45min, finally becomes purple red, TLC spot plate shows that the raw material spot disappears after 1h, and the reaction is stopped after 2 h. The solvent was dried by spinning, the product was extracted with chloroform and water, and anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol were removed with water. The lower layer in the separating funnel is an organic phase, the upper layer is a water phase, the organic phase is purple red, and the water phase is pink. And (3) spin-drying the extracted trichloromethane solution to obtain a 1-vinyl-7-Br-perylene bisimide derivative crude product, and performing column chromatography to obtain a product 1-vinyl-7-Br-perylene bisimide derivative.

Example 5

A preparation method of the 1, 7-vinyl-perylene bisimide derivative comprises the following steps:

the imide site bulky substituent access method comprises the following steps:

the crude product PTCDA-Br was charged in a 250mL three-necked flask

(4.5 mmol), glacial acetic acid (1695l, 140mmol). Heating to 85 ℃ under the protection of nitrogen, and continuing the reaction for 7 hours. After the reaction was completed, it was cooled to room temperature, and then 120.00mL of methanol was added thereto, followed by stirring overnight. And (4) carrying out suction filtration to obtain a red solid, carrying out vacuum drying for 24h, and carrying out column chromatography at 85 ℃ to obtain 1,7-Br-PDI-X.

(0.25 mmol) is added into the system, and the color change of the system is closely concerned in the whole reaction processTLC spot plate observation was performed every 15 min.

The system becomes orange red after 15min, becomes bright red after 30min, becomes dark red after 45min, finally becomes purple red, TLC point plate shows that the raw material point disappears at 1h, and the reaction is stopped after 2 h. After the solvent is dried by spinning, the product is extracted by trichloromethane and water, and anhydrous potassium carbonate, 18-crown-6-ether and unreacted 3-buten-1-ol in the system are removed by water. The lower layer in the separating funnel is an organic phase, the upper layer is a water phase, the organic phase is purple red, and the water phase is pink. And spin-drying the extracted trichloromethane solution to obtain a crude product of the 1-vinyl-7-Br-perylene bisimide derivative, and performing column chromatography to obtain a product of the 1-vinyl-7-Br-perylene bisimide derivative.

Example 6

the imide site bulky substituent access method comprises the following steps:

the crude product PTCDA-Br was charged in a 250mL three-necked flask

(0.50g, 0.91mmol) and 15.00mL of 1-methyl-2-pyrrolidone (NMP) and the solid was dissolved and stirred at 25 ℃ for 1h. Is then added

R is isooctyl (4.5 mmol), glacial acetic acid (1695 ml, 140mmol). The temperature is raised to 85 ℃ under the protection of nitrogen, and the reaction is continued for 7h. After the reaction was completed, it was cooled to room temperature, and then 120.00mL of methanol was added thereto, followed by stirring overnight. And (4) carrying out suction filtration to obtain a red solid, carrying out vacuum drying for 24h, at 85 ℃, and carrying out column chromatography to obtain 1,7-Br-PDI-X.

Example 7

A polystyrene cross-linked fluorescent microsphere with variable colors is prepared by the following steps:

(1) Mixing styrene, a 1-vinyl-7-Br-perylene imide derivative (prepared in example 1) and a peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1;

(2) Adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under stirring, heating to 75 ℃ within 2 minutes, continuing for 5 hours, and stopping reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 0.5; (3) Adding a demulsifier (sodium chloride) into the emulsion under the condition of stirring, filtering after stirring and coagulation, washing with hot water, and drying to obtain the polystyrene cross-linked fluorescent microsphere with variable color; wherein the mass ratio of the demulsifier to the styrene is 1.2.

The finally prepared polystyrene cross-linked fluorescent microsphere with variable colors is a dimer of 1-vinyl-7-Br-perylene bisimide derivatives (namely, two 1-vinyl-7-Br-perylene bisimide derivatives are bonded through pi-pi interaction between perylene core structures of the derivativesSynthesized to form a dimer having a fixed arrangement structure and having two vinyl structures) as a crosslinking agent, the average diameter of the variable-color polystyrene crosslinked fluorescent microspheres is 150nm, the pore diameter variance is 0.9, and the specific surface area is 750m ² g ^-1 The fluorescence quantum yield is 60%; the color-changeable polystyrene cross-linked fluorescent microsphere shows color change along with the infiltration amount of an organic solvent under a certain temperature condition, and specifically comprises the following steps: when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange red; or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; or when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange yellow; after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red; the color change also comprises the peak value change of an emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable under the excitation of the wavelength of 440-460 nm and the fluorescence color change of the color of the polystyrene cross-linked fluorescent microsphere with the color changeable (as shown in figure 1, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a compact dimer state at normal temperature, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable is 645-655 nm, and the fluorescence color of the microsphere is deep red (A); when the organic solvent is soaked in a small amount of organic solvent and placed at the temperature of 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a loose intermediate state (the intermolecular distance is larger than a dimer state and smaller than a monomolecular state), the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is blue-shifted by 5-8 nm, the fluorescence color of the microsphere is orange red (B), when the organic solvent is soaked in a small amount and placed at the temperature of 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a loose monomolecular state, the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow (C), and when the organic solvent is soaked in a large amount, the organic solvent is used for preparing the fluorescent microsphereWhen the polystyrene cross-linked fluorescent microsphere is in an infiltrated normal-temperature state, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable colors is 10-15 nm, and the fluorescence color of the microsphere is orange yellow; after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered to deep red).

Example 8

(1) Mixing styrene, a 1-vinyl-7-Br-perylene imide derivative (prepared from example 5) and a peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1;

(2) Adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under stirring, heating to 75 ℃ within 2 minutes, continuing for 6 hours, and stopping reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 0.7; (3) And adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere, wherein the mass ratio of the demulsifier to the styrene is 2.3.

The finally prepared variable-color polystyrene cross-linked fluorescent microsphere is a polystyrene microsphere taking dimer of 1-vinyl-7-Br-perylene bisimide derivatives (namely, the dimer of two 1-vinyl-7-Br-perylene bisimide derivatives which are combined through pi-pi interaction between perylene core structures thereof to form a dimer with a fixed arrangement structure and two vinyl structures) as a cross-linking agent, and the average diameter of the variable-color polystyrene cross-linked fluorescent microsphere is 182nm, the pore diameter variance is 1.2, and the specific surface area is 760m ² g ^-1 The fluorescence quantum yield is 62%; the color-changeable polystyrene cross-linked fluorescent microsphere shows color change along with the infiltration amount of an organic solvent under a certain temperature condition, and specifically comprises the following steps: polystyrene cross-linked in the presence of small amount of organic solventThe color of the fluorescent microsphere is changed from deep red to orange red; or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the polystyrene cross-linked fluorescent microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; or, when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere capable of changing color changes from deep red to orange yellow; after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red; the color change also comprises the peak value change of an emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable under the excitation of the wavelength of 440-460 nm and the fluorescence color change of the color of the polystyrene cross-linked fluorescent microsphere with the color changeable (as shown in figure 1, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a compact dimer state at normal temperature, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable is 645-655 nm, and the fluorescence color of the microsphere is deep red (A); when a small amount of organic solvent is soaked in the normal temperature state, the 1-vinyl-7-Br-perylene imide derivative at the crosslinking point is in a loose intermediate state (the intermolecular distance is larger than a dimer state and smaller than a monomolecular state), the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 5-8 nm, the fluorescence color of the microsphere is orange red (B), when a small amount of organic solvent is soaked and placed at 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivative at the crosslinking point is in a loose monomolecular state, the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow (C), when a large amount of organic solvent is soaked in the normal temperature state, the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow at the normal temperature, the emission peak of the polystyrene crosslinking fluorescent microsphere with variable color is recovered after the organic solvent is removed and recovered for 1-2 min, the peak value is recovered to 645-655 nm, and the fluorescence color of the color-changeable polystyrene cross-linked fluorescence microsphere is recovered to deep red).

Example 9

(1) Mixing styrene, a 1-vinyl-7-Br-perylene imide derivative (prepared in example 2) and a peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 1;

(2) Adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under the stirring condition, heating to 78 ℃ within 3 minutes, and stopping the reaction after 3 hours to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 1.2; (3) And adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere, wherein the mass ratio of the demulsifier to the styrene is 3.8.

The finally prepared color-changeable polystyrene cross-linked fluorescent microsphere is a polystyrene microsphere taking dimer of 1-vinyl-7-Br-perylene bisimide derivatives (namely, the dimer of two 1-vinyl-7-Br-perylene bisimide derivatives which are combined through pi-pi interaction between perylene core structures thereof to form a dimer with a fixed arrangement structure and two vinyl structures) as a cross-linking agent, the average diameter of the color-changeable polystyrene cross-linked fluorescent microsphere is 203nm, the pore diameter variance is 1.5, and the specific surface area is 764m ² g ^-1 The fluorescence quantum yield is 63%; the color-changeable polystyrene cross-linked fluorescent microsphere shows color change along with the infiltration amount of an organic solvent under a certain temperature condition, and specifically comprises the following components: when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange red; or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the polystyrene cross-linked fluorescent microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; or when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange yellow; after removing the organic solvent and recovering the normal temperature for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red; the change of the color of the presentationThe method also comprises the steps that the peak value of an emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the changeable color is changed under the excitation of the wavelength of 440-460 nm, and the fluorescence color of the polystyrene cross-linked fluorescent microsphere with the changeable color is changed (as shown in figure 1, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a compact dimer state at normal temperature, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the changeable color is 645-655 nm, and the fluorescence color of the microsphere is deep red (A); when a small amount of organic solvent is used for soaking in the normal temperature state, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a loose intermediate state (the intermolecular distance is larger than a dimer state and smaller than a monomolecular state), the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is blue-shifted by 5-8 nm, the fluorescence color of the microsphere is orange red (B), when a small amount of organic solvent is used for soaking and is placed at 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a loose monomolecular state, the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow (C), when a large amount of organic solvent is used for soaking in the normal temperature state, the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow, the emission peak of the polystyrene cross-linked fluorescent microsphere with variable color is recovered after the organic solvent is removed and the normal temperature state is recovered for 1-2 min, the peak value is restored to 645 nm to 655nm, and the fluorescent color of the color-changeable polystyrene cross-linked fluorescent microsphere is restored to deep red).

Example 10

(1) Mixing styrene, a 1-vinyl-7-Br-perylene imide derivative (prepared in example 3) and a peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 1;

(2) Adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under stirring, heating to 80 ℃ within 3 minutes, continuing for 3 hours, and stopping reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 2.2; (3) And adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere, wherein the mass ratio of the demulsifier to styrene is 4.

The finally prepared color-changeable polystyrene cross-linked fluorescent microsphere is a polystyrene microsphere taking dimer of 1-vinyl-7-Br-perylene bisimide derivatives (namely, the dimer of two 1-vinyl-7-Br-perylene bisimide derivatives which are combined through pi-pi interaction between perylene core structures thereof to form a dimer with a fixed arrangement structure and two vinyl structures) as a cross-linking agent, the average diameter of the color-changeable polystyrene cross-linked fluorescent microsphere is 256nm, the pore diameter variance is 1.2, and the specific surface area is 772m ² g ^-1 The fluorescence quantum yield is 77%; the color-changeable polystyrene cross-linked fluorescent microsphere shows color change along with the infiltration amount of an organic solvent under a certain temperature condition, and specifically comprises the following steps: when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange red; or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the polystyrene cross-linked fluorescent microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; or, when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere capable of changing color changes from deep red to orange yellow; after removing the organic solvent and recovering the normal temperature for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red; the color change also comprises the peak value change of an emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable under the excitation of the wavelength of 440-460 nm and the color change of the polystyrene cross-linked fluorescent microsphere with the color changeable (as shown in figure 1, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a compact dimer state at normal temperature, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable is 645-655 nm, the fluorescence color of the microsphere is deep red (A), and the color change is carried out in the presence of a small amount of organic substancesWhen the polystyrene cross-linked fluorescent microspheres are soaked in a solvent at a normal temperature, the 1-vinyl-7-Br-perylene imide derivatives at the cross-linking points are in a loose intermediate state (the intermolecular distance is greater than that of a dimer state and smaller than that of a single molecule state), the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microspheres with variable colors is blue-shifted by 5-8 nm, and the fluorescence color of the microspheres is orange red (B); when the polystyrene cross-linked fluorescent microspheres are soaked in a small amount of organic solvent and placed at the temperature of 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivatives at the cross-linking points are in a loose monomolecular state, the blue shift of an emission peak in a solid fluorescence spectrum of the color-changeable polystyrene cross-linked fluorescent microspheres is 10-15 nm, and the fluorescence color of the microspheres is orange yellow (C); when the microsphere is soaked in a large amount of organic solvent at normal temperature, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is 10-15 nm, and the fluorescence color of the microsphere is orange yellow; after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered to deep red).

Example 11

(1) Mixing styrene, a 1-vinyl-7-Br-perylene imide derivative (prepared in example 1) and a peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 1;

(2) Adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under the stirring condition, heating to 80 ℃ within 3 minutes, continuing for 4 hours, and stopping the reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 2; (3) And adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere, wherein the mass ratio of the demulsifier to styrene is 6.

The final color-changeable polystyrene cross-linked fluorescent microsphere is prepared with 1-vinyl-7-Br-peryleneThe polystyrene microsphere takes dipolymer of imide derivative (namely two 1-vinyl-7-Br-perylene imide derivatives are combined through pi-pi interaction between perylene core structures to form dipolymer with fixed arrangement structure and two vinyl structures) as a cross-linking agent, the average diameter of the polystyrene cross-linked fluorescent microsphere with variable color is 280nm, the pore diameter variance is 1.4, and the specific surface area is 783m ² g ^-1 The fluorescence quantum yield is 78%; the color-changeable polystyrene cross-linked fluorescent microsphere shows color change along with the infiltration amount of an organic solvent under a certain temperature condition, and specifically comprises the following steps: when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange red; or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; or, when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere capable of changing color changes from deep red to orange yellow; after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red; the color change also comprises the peak value change of an emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable under the excitation of the wavelength of 440-460 nm and the color change of the polystyrene cross-linked fluorescent microsphere with the color changeable (as shown in figure 1, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable is 645-655 nm and the fluorescence color of the microsphere is deep red (A) in a normal temperature state, when a small amount of organic solvent is infiltrated in the normal temperature state, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a loose intermediate state (the intermolecular distance is larger than the dimer state and smaller than the monomolecular state), the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable is blue shifted by 5-8 nm and the fluorescence color of the microsphere is orange red (B), when a small amount of organic solvent is infiltrated and is placed at the temperature of 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a loose molecular state and the perylene derivative with the single molecular color changeable polystyrene cross-linked fluorescent microsphere with the perylene molecule stateThe blue shift of the emission peak in the solid fluorescence spectrum of the cross-linked fluorescent microsphere is 10-15 nm, and the fluorescence color of the microsphere is orange yellow (C); when the microsphere is soaked in a large amount of organic solvent at normal temperature, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is 10-15 nm, and the fluorescence color of the microsphere is orange yellow; after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered to deep red).

Example 12

(1) Mixing styrene, a 1-vinyl-7-Br-perylene imide derivative (prepared in example 3) and a peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1;

(2) Adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under stirring, heating to 85 ℃ within 4 minutes, continuing for 2 hours, and stopping reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 2.8; (3) And adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere, wherein the mass ratio of the demulsifier to the styrene is 5.2.

The finally prepared color-changeable polystyrene cross-linked fluorescent microsphere is a polystyrene microsphere taking dimer of 1-vinyl-7-Br-perylene bisimide derivatives (namely, the dimer of two 1-vinyl-7-Br-perylene bisimide derivatives which are combined through pi-pi interaction between perylene core structures thereof to form a dimer with a fixed arrangement structure and two vinyl structures) as a cross-linking agent, the average diameter of the color-changeable polystyrene cross-linked fluorescent microsphere is 323nm, the pore diameter variance is 0.9, and the specific surface area is 780m ² g ^-1 The fluorescence quantum yield is 80%; color-changeable polystyrene cross-linked fluorescent microsphere under certain temperature conditionThe color change is presented along with the infiltration amount of the organic solvent, and the method specifically comprises the following steps: when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange red; or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the polystyrene cross-linked fluorescent microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; or when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange yellow; after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red; the color change also comprises the peak value change of an emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable under the excitation of the wavelength of 440-460 nm and the fluorescence color change of the color of the polystyrene cross-linked fluorescent microsphere with the color changeable (as shown in figure 1, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a compact dimer state at normal temperature, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable is 645-655 nm, and the fluorescence color of the microsphere is deep red (A); when a small amount of organic solvent is soaked in the normal temperature state, the 1-vinyl-7-Br-perylene imide derivative at the crosslinking point is in a loose intermediate state (the intermolecular distance is larger than a dimer state and smaller than a monomolecular state), the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 5-8 nm, the fluorescence color of the microsphere is orange red (B), when a small amount of organic solvent is soaked and placed at 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivative at the crosslinking point is in a loose monomolecular state, the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow (C), when a large amount of organic solvent is soaked in the normal temperature state, the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow at the normal temperature, the emission peak of the polystyrene crosslinking fluorescent microsphere with variable color is recovered after the organic solvent is removed and recovered for 1-2 min, polystyrene cross-linked fluorescent microsphere with peak value restored to 645-655 nm and changeable colorFluorescent color of the color returns to deep red).

Example 13

(1) Mixing styrene, a 1-vinyl-7-Br-perylene imide derivative (prepared in example 6) and a peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 1;

(2) Adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under stirring, heating to 88 ℃ within 4 minutes, continuing for 2 hours, and stopping reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 3.5; (3) And adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere, wherein the mass ratio of the demulsifier to styrene is 6.9.

The finally prepared color-changeable polystyrene cross-linked fluorescent microsphere is a polystyrene microsphere taking dimer of 1-vinyl-7-Br-perylene bisimide derivatives (namely, the dimer of two 1-vinyl-7-Br-perylene bisimide derivatives which are combined through pi-pi interaction between perylene core structures thereof to form a dimer with a fixed arrangement structure and two vinyl structures) as a cross-linking agent, the average diameter of the color-changeable polystyrene cross-linked fluorescent microsphere is 365nm, the pore diameter variance is 1.2, and the specific surface area is 800m ² g ^-1 The fluorescence quantum yield is 71%; the color-changeable polystyrene cross-linked fluorescent microsphere shows color change along with the infiltration amount of an organic solvent under a certain temperature condition, and specifically comprises the following steps: when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange red; or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the polystyrene cross-linked fluorescent microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; or, the color of the polystyrene crosslinking fluorescent microsphere capable of changing color changes from deep red to orange yellow at normal temperature when a large amount of organic solvent is added(ii) a After the organic solvent is removed and the normal temperature is recovered for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red; the color change also comprises the peak value change of an emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable under the excitation of the wavelength of 440-460 nm and the fluorescence color change of the color of the polystyrene cross-linked fluorescent microsphere with the color changeable (as shown in figure 1, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a compact dimer state at normal temperature, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable is 645-655 nm, and the fluorescence color of the microsphere is deep red (A); when a small amount of organic solvent is soaked in the normal temperature state, the 1-vinyl-7-Br-perylene imide derivative at the crosslinking point is in a loose intermediate state (the intermolecular distance is larger than a dimer state and smaller than a monomolecular state), the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 5-8 nm, the fluorescence color of the microsphere is orange red (B), when a small amount of organic solvent is soaked and placed at 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivative at the crosslinking point is in a loose monomolecular state, the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow (C), when a large amount of organic solvent is soaked in the normal temperature state, the emission peak in the solid fluorescence spectrum of the polystyrene crosslinking fluorescent microsphere with variable color is blue-shifted by 10-15 nm, the fluorescence color of the microsphere is orange yellow at the normal temperature, the emission peak of the polystyrene crosslinking fluorescent microsphere with variable color is recovered after the organic solvent is removed and recovered for 1-2 min, the peak value is recovered to 645-655 nm, and the fluorescence color of the color-changeable polystyrene cross-linked fluorescence microsphere is recovered to deep red).

Example 14

(1) Mixing styrene, a 1-vinyl-7-Br-perylene imide derivative (prepared in example 4) and a peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of the dibenzoyl peroxide to the styrene is 1;

(2) Adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under stirring, heating to 90 ℃ within 5 minutes, continuing for 2 hours, and stopping reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 3.8; (3) And adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying to obtain the color-changeable polystyrene cross-linked fluorescent microsphere, wherein the mass ratio of the demulsifier to the styrene is 8.

The finally prepared variable-color polystyrene cross-linked fluorescent microsphere is a polystyrene microsphere taking dimer of 1-vinyl-7-Br-perylene bisimide derivatives (namely, the dimer of two 1-vinyl-7-Br-perylene bisimide derivatives which are combined through pi-pi interaction between perylene core structures thereof to form a dimer with a fixed arrangement structure and two vinyl structures) as a cross-linking agent, and the average diameter of the variable-color polystyrene cross-linked fluorescent microsphere is 400nm, the pore diameter variance is 1.8, and the specific surface area is 750m ² g ^-1 The fluorescence quantum yield is 65%; the color-changeable polystyrene cross-linked fluorescent microsphere shows color change along with the infiltration amount of an organic solvent under a certain temperature condition, and specifically comprises the following components: when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange red; or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the polystyrene cross-linked fluorescent microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent; or when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange yellow; after removing the organic solvent and recovering the normal temperature for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red; the color change also comprises the peak value change of an emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable under the excitation of the wavelength of 440-460 nm and the fluorescence color change of the color of the polystyrene cross-linked fluorescent microsphere with the color changeable (as shown in figure 1, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a compact dimer state at the normal temperature state, and the color changeable polystyrene cross-linked fluorescent microsphere isThe peak value of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere is 645-655 nm, and the fluorescence color of the microsphere is deep red (A); when the polystyrene cross-linked fluorescent microsphere is soaked in a small amount of organic solvent at normal temperature, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a loose intermediate state (the intermolecular distance is larger than that of a dimer state and smaller than that of a single molecule state), the emission peak in the solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is blue-shifted by 5-8 nm, and the fluorescence color of the microsphere is orange red (B); when the polystyrene cross-linked fluorescent microsphere is soaked in a small amount of organic solvent and is placed at the temperature of 40-50 ℃, the 1-vinyl-7-Br-perylene imide derivative at the cross-linking point is in a loose monomolecular state, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is 10-15 nm, and the fluorescence color of the microsphere is orange yellow (C); when the microsphere is soaked in a large amount of organic solvent at normal temperature, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is 10-15 nm, and the fluorescence color of the microsphere is orange yellow; after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered to deep red).

Claims

1. A polystyrene cross-linked fluorescent microsphere with variable colors is characterized in that: the color-changeable polystyrene cross-linked fluorescent microsphere is a polystyrene microsphere taking a dimer of 1-vinyl-7-Br-perylene bisimide derivatives as a cross-linking agent;

the dimer of the 1-vinyl-7-Br-perylene bisimide derivative is formed by combining two 1-vinyl-7-Br-perylene bisimide derivatives through pi-pi interaction between perylene core structures of the two 1-vinyl-7-Br-perylene bisimide derivatives to form a dimer which has a fixed arrangement structure and two vinyl structures;

the 1-vinyl-7-Br-perylene bisimide derivative is perylene bisimide which has ethylene groups at the 1 position and Br atom substituents at the 7 position in the gulf positions (1, 7 positions) and is connected with bulky substituents at the imide positions;

the color-changeable polystyrene cross-linked fluorescent microsphere shows color change along with the infiltration amount of an organic solvent under a certain temperature condition, and the organic solvent is a good solvent of the 1-vinyl-7-Br-perylene bisimide derivative.

2. The polystyrene cross-linked fluorescent microsphere with variable color according to claim 1, wherein the polystyrene cross-linked fluorescent microsphere with variable color shows color change with the infiltration amount of the organic solvent under a certain temperature condition specifically means that:

when a small amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange red;

or, the color of the polystyrene cross-linked fluorescent microsphere with variable color changes from deep red to orange yellow when the microsphere is placed at the temperature of 40-50 ℃ and is in a state of being soaked by a small amount of organic solvent;

or when a large amount of organic solvent is added at normal temperature, the color of the polystyrene cross-linked fluorescent microsphere with variable color is changed from deep red to orange yellow;

after removing the organic solvent and recovering the normal temperature for 1-2 min, the color of the polystyrene cross-linked fluorescent microsphere with variable color is recovered to be deep red;

all organic solvents are selected from tetrahydrofuran, dichloromethane and toluene;

all the small amount of organic solvent refers to the volume ratio of the polystyrene crosslinking fluorescent microspheres with variable colors to the organic solvent is 1;

all the organic solvents refer to the volume ratio of the polystyrene crosslinking fluorescent microspheres with variable colors to the organic solvents is 1.1-10.

3. The color-changeable polystyrene crosslinked fluorescent microsphere according to claim 2, wherein the color change further comprises a change in the peak value of the emission peak in the solid fluorescence spectrum of the color-changeable polystyrene crosslinked fluorescent microsphere under excitation at a wavelength of 440-460 nm and a change in the fluorescence color of the color-changeable polystyrene crosslinked fluorescent microsphere:

the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with the color changeable at the normal temperature state is 645-655 nm; the fluorescence color of the microsphere is deep red;

when the polystyrene cross-linked fluorescent microsphere is in a normal temperature state of being soaked by a large amount of organic solvents, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene cross-linked fluorescent microsphere with variable color is 10-15 nm; the fluorescence color of the microsphere is orange yellow;

after the organic solvent is removed and the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the color-changeable polystyrene cross-linked fluorescent microsphere is recovered to deep red.

4. The color-changeable polystyrene cross-linked fluorescent microsphere of claim 1, wherein the bulky substituent is a silsesquioxane or a long alkyl chain with side chains;

the silsesquioxane is

R is isobutyl or isooctyl;

the long alkyl chain with side chain is

Wherein

5. A variable according to claim 1The colored polystyrene crosslinked fluorescent microsphere is characterized in that the average diameter of the colored polystyrene crosslinked fluorescent microsphere is 150-400 nm, the pore diameter variance is 0.9-1.8, and the specific surface area is 750-800 m ² g ^-1 The yield of fluorescence quantum is 60-80%.

6. The method for preparing polystyrene cross-linked fluorescent microsphere with variable color as claimed in any one of claims 1 to 5, characterized in that the method comprises the following steps:

7. The method for preparing a polystyrene cross-linked fluorescent microsphere with variable colors according to claim 6, wherein the mass ratio of the peroxide initiator to the styrene is 1; the molar ratio of the styrene to the 1-vinyl-7-Br-perylene imide derivative is 5-6; the peroxide initiator is dibenzoyl peroxide.

8. The method for preparing color-changeable polystyrene crosslinked fluorescent microspheres according to claim 6, wherein the rapid temperature rise is a temperature rise within 5 minutes, T is 75-90 ℃, and the period of time is 2-6 hours.

9. The method for preparing color-changeable polystyrene cross-linked fluorescent microspheres of claim 6, wherein the emulsion is sodium dodecyl sulfate, and the mass ratio of the emulsion to styrene is 0.5-3.

10. The method for preparing the polystyrene cross-linked fluorescent microsphere with variable color according to claim 6, wherein the demulsifier is sodium chloride, and the mass ratio of the demulsifier to the styrene is 1.2-8.