CN111979603A

CN111979603A - Temperature reversible response PET fiber with low addition amount of functional material and preparation method thereof

Info

Publication number: CN111979603A
Application number: CN202010670323.7A
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: 2020-11-24
Anticipated expiration: 2040-07-13
Also published as: CN111979603B

Abstract

The invention relates to a temperature reversible response PET fiber with low addition of functional materials and a preparation method thereof, wherein polystyrene microspheres/PET master batches and PET are subjected to skin-core composite spinning to prepare a temperature reversible response POY (polyester oriented yarn) filament under a POY (polyester oriented yarn) process, and the temperature reversible response POY filament is subjected to texturing under a DTY (draw texturing yarn) process to prepare the temperature reversible response PET fiber; polystyrene high-fluorescence microspheres are dispersed in the skin layer of the prepared temperature reversible response PET fiber; the polystyrene high-fluorescence microsphere is formed by combining two 1-vinyl-7-Br-perylene bisimide derivatives through pi-pi interaction between perylene core structures of the derivatives to form a dimer which has a fixed arrangement structure and two vinyl structures and is used as a cross-linking agent; when the temperature of the PET fiber is higher than 50-100 ℃, the color of the fiber is changed from deep red to orange yellow, the fluorescence emission peak is blue-shifted from 645-655 nm by 10-15 nm under the excitation of 460nm, the color of the fiber is restored to deep red after the temperature is reduced to below 50 ℃ in 2min, and the fluorescence emission peak is restored to 645-655 nm.

Description

Temperature reversible response PET fiber with low addition amount of functional material and preparation method thereof

Technical Field

The invention belongs to the technical field of temperature response materials, and relates to a temperature reversible response PET fiber with low addition of functional materials and a preparation method thereof.

Background

Temperature responsive materials refer to a class of materials whose properties change as a function of temperature. The temperature response mechanism is mainly that the temperature is changed to enable the temperature response material occupying the key sites in the material to generate chemical bond change or aggregation state change, so that the property change of the material, such as color, mechanical property or transparency, is initiated. It is often used as an intelligent 'switch' and is applied to the fields of sensors, biomedicine or chemistry and biocatalysis and the like. The temperature response material has wide application scenes and large demand because the temperature is easy to regulate and control, and has obtained wide attention and research.

However, the existing temperature response material is usually based on a specific temperature response material, is prepared in a small scale in a laboratory through precise design and synthesis, and often does not have industrial potential and cost performance. This is because the temperature-responsive material often needs to occupy the "key site" of the material to exert its temperature-responsive characteristics, and therefore, a precise design is required, which puts a severe demand on the control of the reaction conditions in the industrial production, and thus the industrial preparation of the temperature-responsive material is rare.

The existing temperature response fiber preparation method mainly comprises the following steps: mixing the temperature response material with the raw material, and then spinning or adopting hollow fiber to dip and fill; the former is affected by preparation technology, the filling amount of the temperature response material is not high, the temperature response capability is limited, and the latter is difficult to package. For example, outlast fiber provided by outlast is the main brand of temperature response fiber in the market, the preparation method is mainly mixed spinning, the filling amount of the temperature response material is lower than 20%, and the temperature response capability is extremely low; whereas the method of impregnation filling with hollow fibers is limited by the edge position of the encapsulation technology already on the market.

The thermochromic material in the temperature-responsive material is a material capable of changing color in response to a change in temperature, and has a colored form and a colorless form. When the temperature is lower than a certain temperature value, the thermochromic material takes one form; when the temperature is higher than the temperature value, the other form is presented.

The self-assembly behavior of the environment-responsive multi-block copolymer in a specific environment has the responsiveness and sensitivity of an external environment, and is a hot spot in the research field of polymer science and surface interface chemistry at present. Self-assembly of a polymer refers to the process by which molecules spontaneously build aggregates with specific structures and shapes under the impetus of weak interaction forces such as hydrogen bonding, electrostatic interactions, van der waals forces, and the like. Amphiphilic multiblock polymers possess segments that have an affinity for both the aqueous and oil phases. In solution, the synergy of the two blocks allows the polymer to self-assemble into molecular aggregates with abundant morphological structures. Temperature responsive multi-block polymers are one of the important branches of environmentally responsive polymers.

In the prior art, poly (N-isopropylacrylamide) (PNIPAM) is used as a fiber-forming polymer, tetrahydrofuran is used as a solvent to prepare a spinning solution, and the temperature-responsive nanofiber is prepared by an electrostatic spinning process; wherein, because a cross-linking structure is not formed among PNIPAM molecular chains in the fiber, the PNIPAM molecular chains can be quickly dissolved in water at room temperature, and the application value is not high. In subsequent researches, units capable of forming a physical structure and a chemical crosslinking structure are respectively introduced into a PNIPAM molecular chain by a free radical copolymerization method, and then the temperature-responsive nanofiber with good stability in an aqueous medium is prepared by adopting an electrostatic spinning method or combining with a heat treatment process; however, the electrospun nanofibers are often non-woven fabrics, have low strength and are difficult to meet the requirements of various occasions.

The prior art also discloses a temperature-sensitive color-changing fabric which is formed by interweaving warp yarns and weft yarns, wherein the warp yarns are polytrimethylene terephthalate fiber filaments containing temperature-sensitive color-changing capsules, the weft yarns are common polytrimethylene terephthalate fiber filaments, the color change rule of the fabric is red, orange and yellow, the three colors continuously change along with the external temperature, and reversible color change is realized; but the preparation process of the color-changing capsule is complex.

Disclosure of Invention

The invention provides a temperature reversible response PET fiber with low addition of functional materials and a preparation method thereof, aiming at solving the problems in the prior art;

one of the purposes of the invention is to provide a preparation method of a temperature reversible response PET fiber with low addition of functional materials, which adopts PET fiber with polystyrene high-fluorescence microspheres dispersed in a skin layer prepared by skin-core composite spinning; the polystyrene high-fluorescence microsphere is formed by combining two 1-vinyl-7-Br-perylene bisimide derivatives through pi-pi interaction between perylene core structures of the derivatives to form a dimer which has a fixed arrangement structure and two vinyl structures and is used as a cross-linking agent;

the invention also aims to provide the temperature reversible response PET fiber with low addition of functional materials, when the temperature of the PET fiber is higher than 50-100 ℃, the color of the fiber is changed from deep red to orange yellow, the fluorescence emission peak is blue-shifted from 645-655 nm by 10-15 nm under the excitation of 460nm, the color of the fiber is restored to deep red after the temperature is reduced to below 50 ℃ in 2min, and the fluorescence emission peak is restored to 645-655 nm.

In order to achieve the purpose, the invention adopts the following scheme:

a temperature reversible response PET fiber with low addition of functional materials is a temperature reversible response PET fiber prepared by sheath-core composite spinning; polystyrene high-fluorescence microspheres are dispersed in the skin layer of the temperature reversible response PET fiber;

the polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes a dimer of 1-vinyl-7-Br-perylene bisimide derivatives as a cross-linking agent (note that the fact that the cross-linking agent is a dimer of 1-vinyl-7-Br-perylene bisimide derivatives is emphasized here means that two 1-vinyl-7-Br-perylene bisimide derivatives which form the dimer can be disconnected at normal temperature under special conditions such as high temperature);

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 existence mode of the 1-vinyl-7-Br-perylene bisimide derivative is related to the temperature, when the temperature is higher, the movement of molecules is relatively free, and the distance between dimers of the 1-vinyl-7-Br-perylene bisimide derivative is increased and changes to a monomolecular state. When the temperature is lower, the molecular motion capability is weakened, the molecules are close to each other due to the existence of pi-pi interaction and mostly exist in a dimer mode; and because the bulky group on the imide position of the derivative and the 1-vinyl-7-Br-perylene imide derivative exist at the crosslinking point of the macromolecular crosslinking network, the molecular aggregate stays in a dimer state, and a complex aggregation state is not formed.

The 1-vinyl-7-Br-perylene bisimide derivative is perylene bisimide which is provided with an ethylene 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 long alkyl chain with a side chain at the imide position;

when the temperature of the temperature reversible response PET fiber is higher than 50-100 ℃, the color of the temperature reversible response PET fiber is changed from deep red to orange yellow, the fluorescence emission peak is blue-shifted from 645-655 nm by 10-15 nm under the excitation of 460nm, and the color of the temperature reversible response PET fiber is restored to deep red and the fluorescence emission peak is restored to 645-655 nm after the temperature is reduced to below 50 ℃ for 2 min. The 1-vinyl-7-Br-perylene bisimide derivative has different fluorescence emission corresponding to a dimer state and a monomolecular state, and the emission peak of the dimer state is more biased to long-wavelength emission than that of the monomolecular state.

As a preferred technical scheme:

according to the temperature reversible response PET fiber with the low addition amount of the functional material, the polystyrene high-fluorescence microsphere shows color change under a certain temperature condition, and specifically means that: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; and after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red.

The temperature reversible response PET fiber with the low addition amount of the functional material further comprises the following steps that the color change of fluorescence is the peak value change of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere under the excitation of the wavelength of 440-460 nm, and the color change of the fluorescence of the polystyrene high-fluorescence microsphere is changed:

the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere in a normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red;

when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow;

and after the normal temperature is recovered for 1-2 min, recovering the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere, recovering the peak value to 645-655 nm, and recovering the fluorescence color of the polystyrene high-fluorescence microsphere to deep red.

The temperature reversible response PET fiber with low addition of the functional material has the molecular formula of the 1-vinyl-7-Br-perylene bisimide derivative:

wherein R is₁And R₂Comprises the following steps: when R is₁＝C_nH_2n+1When then R is₂＝C_nH_2n+1And n is more than or equal to 11; when R is₁＝C_nH_2n+1And 11 are>When n is greater than or equal to 7, then R₂＝C_mH_2m+1And 11 are>m≥9。

The temperature reversible response PET fiber with low addition of functional materials has the advantages that the average diameter of the polystyrene high-fluorescence microsphere is 150-400 nm, the pore diameter variance is 0.9-1.8, and the specific surface area is 750-800 m²g^-1The yield of the fluorescence quantum is 60-80%.

The invention also provides a preparation method of the temperature reversible response PET fiber with low addition of the functional material, which comprises the steps of carrying out skin-core composite spinning on two components of the polystyrene microsphere/PET master batch and the PET, specifically, carrying out spinning under a POY process by taking the PET as a core layer component and the polystyrene microsphere/PET master batch as a skin layer component to prepare a temperature reversible response POY filament, and then carrying out texturing on the temperature reversible response POY filament under a DTY process to prepare the temperature reversible response PET fiber;

the preparation process of the polystyrene microsphere/PET master batch comprises the following steps:

adding low-melting-point PET powder and polystyrene high-fluorescence microspheres into a mixer for mixing, and performing melt extrusion on the mixed components through a screw extruder to obtain polystyrene microspheres/PET master batches;

the preparation method of the polystyrene high-fluorescence microsphere 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 condition of stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microspheres.

As a preferred technical scheme:

according to the preparation method of the temperature reversible response PET fiber with the low addition amount of the functional material, in the preparation of the polystyrene high-fluorescence microsphere, the mass ratio of the peroxide initiator to the styrene is 1: 75-85; the molar ratio of the styrene to the 1-vinyl-7-Br-perylene imide derivative is 5-6: 1; the peroxide initiator is dibenzoyl peroxide (BPO); the rapid heating is carried out within 5 minutes, T is 75-90 ℃, and the period of time is 2-6 hours; the demulsifier is sodium chloride, and the mass ratio of the demulsifier to styrene is 1.2-8: 80; the emulsion is sodium dodecyl sulfate, and the mass ratio of the emulsion to styrene is 0.5-3: 80.

According to the preparation method of the temperature reversible response PET fiber with the low addition amount of the functional material, the mass ratio of the skin layer to the core layer of the temperature reversible response PET fiber is 1: 0.25-4; in the polystyrene microsphere/PET master batch, the mass fraction of the polystyrene high-fluorescence microsphere is 15-25%; the melting point of the low-melting-point PET powder is 180-220 ℃.

According to the preparation method of the temperature reversible response PET fiber with the low addition of the functional material, in the preparation of the polystyrene microsphere/PET master batch, the rotating speed of a mixer is 55-65 r/min, the mixing time is 30-40 min, the temperature of a screw extruder is 220-250 ℃, and the rotating speed is 300-320 r/min;

the parameters of the POY process are as follows: the temperature of the spinning beam is 2222322 ℃, the temperature of the side blowing is 12222 ℃, the wind speed is 2.121.2m/s, the relative humidity is 22292%, the speed of the first godet is 222223222m/min, the speed of the second godet is 222223222m/min, and the winding speed is 222223222 m/min;

the DTY process comprises the following steps: feeding the temperature reversible response POY yarn into a first roller, and preparing the temperature reversible response PET fiber through a yarn guide porcelain I, a hot box, a yarn guide porcelain II, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot; the temperature of the hot box is 140-180 ℃.

The principle of the invention is as follows:

the high cost of synthesis of temperature responsive materials increases the cost of the fiber when applied to temperature responsive fibers. The invention adds polystyrene fluorescent microspheres with temperature response performance in the fiber skin layer by a skin-core composite spinning method. The microsphere takes dimer of 1-vinyl-7-Br-perylene bisimide derivative as a cross-linking agent in polystyrene microsphere, the dimer is combined through pi-pi interaction, and each molecule has an ethylene group, and the dimer has two ethylene groups, so that the dimer can become a cross-linking agent of a high molecular network. The dimer formed by pi-pi interaction is sensitive to temperature as a cross-linking point in the microsphere, and can be converted to a monomolecular state at a higher temperature (50-100 ℃ and the specific temperature is related to a molecular structure). 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-changing performance sensitive to temperature. As the pi-pi interaction is a non-covalent weak interaction, the compound has reversible property. When the ambient temperature is reduced (less than 50 ℃) for 2 minutes, the molecules are re-identified through pi-pi interaction and return to the dimer state, and the color thereof includes the color at which the fluorescence color returns to the compact dimer state.

When the microspheres with the properties are used as a part of the PET fiber skin layer, the color of the microspheres is changed to cause the color of the fibers to be changed after the ambient temperature is changed. Because the polystyrene microsphere has a benzene ring structure, the PET matrix also has a benzene ring structure. Therefore, the microsphere has better dispersion performance in PET, is stronger in combination with a matrix, and has smaller influence on the performance of the fiber.

Has the advantages that:

(1) the preparation method of the temperature reversible response PET fiber with low addition of the functional material does not need a complex synthesis technology, the whole preparation process does not generate chemical reaction, the preparation process is simple, the flow is short, and the preparation of large-scale temperature response fibers can be realized; different temperature response fibers can be obtained by adjusting the temperature response material, so that the variety and the application range of the temperature response fibers are greatly expanded;

(2) the temperature reversible response PET fiber with low addition of functional materials has the advantages of temperature response, high fiber strength, good stability and quick response, and can be applied to the fields of temperature sensitive switches, shape memory materials, temperature sensors, intelligent heat insulation materials and the like.

Detailed Description

The invention will be further illustrated with reference to specific 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.

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 dissolved and stirred at 25 ℃ for 1 h. Is then added

(2.25mmol) and

(2.25mmol), glacial acetic acid (16mL,140 mmol). 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 put in a 50mL eggplant-shaped flask, and HPLC-grade THF (20mL) was added thereto and sufficiently dissolved with stirring, and the mixture was heated at 45 ℃ to give an orange-yellow color. Subsequently, anhydrous potassium carbonate (55.4mg,0.40mmol), 18-crown-6-ether (105.73mg,0.40mmol) were added to the system, and the mixture was pipetted off with a pipette

(0.25mmol) 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 turns orange red after 15min, turns bright red after 30min, turns deep red after 45min, and finally turns purple red, TLC spot plate shows that the raw material spot disappears at 1h, and the reaction is stopped after continuing to react for 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 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

(2.25mmol) and

Example 3

The 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

(2.25mmol) and

(0.25mmol) is added into the system, and the whole reaction process is closeThe system color change was noted and one TLC spot plate observation was performed at 15min intervals.

Example 4

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

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

(4.5mmol), glacial acetic acid (16mL,140 mmol). 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.

Example 5

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

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

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

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

Example 7

A preparation method of a temperature reversible response PET fiber with low addition of functional materials comprises the following steps:

(1) preparing polystyrene high-fluorescence microspheres;

(1.1) mixing styrene, 1-vinyl-7-Br-perylene imide derivative (prepared in example 1) and peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1:75, and the molar ratio of styrene to 1-vinyl-7-Br-perylene imide derivative is 5: 1;

(1.2) adding the mixture into deionized water and an emulsion (sodium dodecyl sulfate) under the stirring condition, heating to 75 ℃ for 2 minutes, keeping for 5 hours, stopping the reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 0.5:80(1.3), adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microspheres, wherein the mass ratio of the demulsifier to styrene is 1.2:80

(2) Preparing polystyrene microsphere/PET master batch: adding low-melting-point PET powder (with a melting point of 180 ℃) and polystyrene high-fluorescence microspheres into a mixer for mixing, and carrying out melt extrusion on the mixed components through a screw extruder to prepare polystyrene microsphere/PET master batch, wherein the rotating speed of the mixer is 55r/min, the mixing time is 30min, the temperature of the screw extruder is 234 ℃, the rotating speed is 300r/min, and the mass fraction of the polystyrene high-fluorescence microspheres in the polystyrene microsphere/PET master batch is 15%;

(3) preparing temperature reversible response PET fiber: performing skin-core composite spinning on two components, namely polystyrene microsphere/PET master batch and PET, specifically, spinning by taking PET as a core layer component and polystyrene microsphere/PET master batch as a skin layer component under a POY (polyester pre-oriented yarn) process to prepare temperature reversible response POY (polyester pre-oriented yarn) yarns, and then performing texturing on the temperature reversible response POY yarns under a DTY (draw texturing yarn) process to prepare temperature reversible response PET fibers, wherein the mass ratio of the skin layer to the core layer is 1: 0.25;

the parameters of the POY process are as follows: the temperature of a spinning box body is 250 ℃, the temperature of lateral blowing is 10 ℃, the wind speed is 0.1m/s, the relative humidity is 55 percent, the speed of a first godet is 2500m/min, the speed of a second godet is 2500m/min, and the winding speed is 2500 m/min;

the DTY process comprises the following steps: feeding the temperature reversible response POY yarn into a first roller, and preparing the temperature reversible response PET fiber through a yarn guide porcelain I, a hot box, a yarn guide porcelain II, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot; the temperature of the hot box was 140 ℃.

Polystyrene high-fluorescence microspheres are dispersed in the skin layer of the finally prepared temperature reversible response PET fiber; the polystyrene high-fluorescence microsphere is formed by taking dimer of 1-vinyl-7-Br-perylene bisimide derivative (namely, dimer with two vinyl structures and two fixed arrangement structures formed by combining two 1-vinyl-7-Br-perylene bisimide derivatives through pi-pi interaction between perylene core structures thereof) as a cross-linkingPolystyrene microspheres of the agent, the average diameter of which is 150nm, the pore diameter variance of which is 0.9 and the specific surface area of which is 750m²g^-1The fluorescence quantum yield is 60%; the polystyrene high-fluorescence microsphere shows color change under a certain temperature condition, and specifically comprises the following steps: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red; the present color change further includes a fluorescent color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes; the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere in a normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red; when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow; after the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is recovered to deep red;

when the temperature of the temperature reversible response PET fiber is higher than 50-100 ℃, the color of the temperature reversible response PET fiber is changed from deep red to orange yellow, the fluorescence emission peak is blue-shifted from 645-655 nm by 10-15 nm under the excitation of 460nm, and the color of the temperature reversible response PET fiber is restored to deep red and the fluorescence emission peak is restored to 645-655 nm after the temperature is reduced to below 50 ℃ for 2 min.

Example 8

(1) preparing polystyrene high-fluorescence microspheres;

(1.1) mixing styrene, 1-vinyl-7-Br-perylene imide derivative (prepared in example 2) and peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1:75, and the molar ratio of styrene to 1-vinyl-7-Br-perylene imide derivative is 5: 1;

(1.2) adding deionized water and an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, heating to 75 ℃ within 2 minutes, keeping for 6 hours, and stopping the reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 0.7: 80; (1.3) adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microsphere, wherein the mass ratio of the demulsifier to the styrene is 2.3: 80;

(2) preparing polystyrene microsphere/PET master batch: adding low-melting-point PET powder (with a melting point of 194 ℃) and polystyrene high-fluorescence microspheres into a mixer for mixing, and carrying out melt extrusion on the mixed components through a screw extruder to prepare polystyrene microsphere/PET master batch, wherein the rotating speed of the mixer is 61r/min, the mixing time is 32min, the temperature of the screw extruder is 230 ℃, the rotating speed is 319r/min, and the mass fraction of the polystyrene high-fluorescence microspheres in the polystyrene microsphere/PET master batch is 22%;

(3) preparing temperature reversible response PET fiber: performing skin-core composite spinning on two components, namely polystyrene microsphere/PET master batch and PET, specifically, spinning by taking PET as a core layer component and polystyrene microsphere/PET master batch as a skin layer component under a POY (polyester pre-oriented yarn) process to prepare temperature reversible response POY (polyester pre-oriented yarn) yarns, and then performing texturing on the temperature reversible response POY yarns under a DTY (draw texturing yarn) process to prepare temperature reversible response PET fibers, wherein the mass ratio of the skin layer to the core layer is 1: 0.5;

the parameters of the POY process are as follows: the temperature of the spinning box body is 282 ℃, the temperature of lateral blowing is 37 ℃, the wind speed is 0.2m/s, the relative humidity is 85 percent, the speed of the first godet is 3028m/min, the speed of the second godet is 3028m/min, and the winding speed is 3028 m/min;

the DTY process comprises the following steps: feeding the temperature reversible response POY yarn into a first roller, and preparing the temperature reversible response PET fiber through a yarn guide porcelain I, a hot box, a yarn guide porcelain II, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot; the temperature of the hot box was 155 ℃.

Polystyrene is dispersed in the skin layer of the finally prepared temperature reversible response PET fiberAlkene high fluorescence microspheres; the polystyrene high-fluorescence 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 is 182nm, the pore diameter variance is 1.2, and the specific surface area is 760m²g^-1The fluorescence quantum yield is 62%; the polystyrene high-fluorescence microsphere shows color change under a certain temperature condition, and specifically comprises the following steps: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red; the present color change further includes a fluorescent color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes; the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere in a normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red; when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow; after the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is recovered to deep red;

Example 9

(1) preparing polystyrene high-fluorescence microspheres;

(1.1) mixing styrene, 1-vinyl-7-Br-perylene imide derivative (prepared in example 3) and peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1:78, and the molar ratio of styrene to 1-vinyl-7-Br-perylene imide derivative is 5: 1;

(1.2) adding deionized water and an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, heating to 78 ℃ within 3 minutes, continuing for 3 hours, and stopping the reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 1.2: 80; (1.3) adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microsphere, wherein the mass ratio of the demulsifier to the styrene is 3.8: 80; (2) preparing polystyrene microsphere/PET master batch: adding low-melting-point PET powder (the melting point is 216 ℃) and polystyrene high-fluorescence microspheres into a mixer for mixing, and carrying out melt extrusion on the mixed components through a screw extruder to prepare polystyrene microsphere/PET master batch, wherein the rotating speed of the mixer is 56r/min, the mixing time is 34min, the temperature of the screw extruder is 225 ℃, the rotating speed is 309r/min, and the mass fraction of the polystyrene high-fluorescence microspheres in the polystyrene microsphere/PET master batch is 16%;

(3) preparing temperature reversible response PET fiber: performing skin-core composite spinning on two components, namely polystyrene microsphere/PET master batch and PET, specifically, spinning by taking PET as a core layer component and polystyrene microsphere/PET master batch as a skin layer component under a POY (polyester pre-oriented yarn) process to prepare temperature reversible response POY (polyester pre-oriented yarn) yarns, and then performing texturing on the temperature reversible response POY yarns under a DTY (draw texturing yarn) process to prepare temperature reversible response PET fibers, wherein the mass ratio of the skin layer to the core layer is 1: 1;

the parameters of the POY process are as follows: the temperature of the spinning box body is 260 ℃, the temperature of the side blowing is 14 ℃, the wind speed is 0.36m/s, the relative humidity is 67%, the speed of the first godet is 3397m/min, the speed of the second godet is 3397m/min, and the winding speed is 3397 m/min;

the DTY process comprises the following steps: feeding the temperature reversible response POY yarn into a first roller, and preparing the temperature reversible response PET fiber through a yarn guide porcelain I, a hot box, a yarn guide porcelain II, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot; the temperature of the hot box was 141 ℃.

Polystyrene high-fluorescence microspheres are dispersed in the skin layer of the finally prepared temperature reversible response PET fiber; the polystyrene high-fluorescence 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 is 203nm, the pore diameter variance is 1.5, and the specific surface area is 764m²g^-1The fluorescence quantum yield is 63%; the polystyrene high-fluorescence microsphere shows color change under a certain temperature condition, and specifically comprises the following steps: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red; the present color change further includes a fluorescent color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes; the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere in a normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red; when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow; after the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is recovered to deep red;

Example 10

(1) preparing polystyrene high-fluorescence microspheres;

(1.1) mixing styrene, 1-vinyl-7-Br-perylene imide derivative (prepared in example 6) and peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1:80, and the molar ratio of styrene to 1-vinyl-7-Br-perylene imide derivative is 5.5: 1;

(1.2) adding deionized water and an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, heating to 80 ℃ within 3 minutes, continuing for 3 hours, and stopping the reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 2.2: 80; (1.3) adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microsphere, wherein the mass ratio of the demulsifier to the styrene is 4: 80; (2) preparing polystyrene microsphere/PET master batch: adding low-melting-point PET powder (with a melting point of 185 ℃) and polystyrene high-fluorescence microspheres into a mixer for mixing, and carrying out melt extrusion on the mixed components through a screw extruder to prepare polystyrene microsphere/PET master batch, wherein the rotating speed of the mixer is 63r/min, the mixing time is 40min, the temperature of the screw extruder is 244 ℃, the rotating speed is 312r/min, and the mass fraction of the polystyrene high-fluorescence microspheres in the polystyrene microsphere/PET master batch is 16%;

(3) preparing temperature reversible response PET fiber: performing skin-core composite spinning on two components, namely polystyrene microsphere/PET master batch and PET, specifically, spinning by taking PET as a core layer component and polystyrene microsphere/PET master batch as a skin layer component under a POY (polyester pre-oriented yarn) process to prepare temperature reversible response POY (polyester pre-oriented yarn) yarns, and then performing texturing on the temperature reversible response POY yarns under a DTY (draw texturing yarn) process to prepare temperature reversible response PET fibers, wherein the mass ratio of the skin layer to the core layer is 1: 2;

the parameters of the POY process are as follows: the temperature of the spinning box body is 251 ℃, the temperature of the side blowing is 21 ℃, the wind speed is 0.7m/s, the relative humidity is 82 percent, the speed of the first godet is 2588m/min, the speed of the second godet is 2588m/min, and the winding speed is 2588 m/min;

the DTY process comprises the following steps: feeding the temperature reversible response POY yarn into a first roller, and preparing the temperature reversible response PET fiber through a yarn guide porcelain I, a hot box, a yarn guide porcelain II, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot; the temperature of the hot box was 162 ℃.

Polystyrene high-fluorescence microspheres are dispersed in the skin layer of the finally prepared temperature reversible response PET fiber; the polystyrene high-fluorescence 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 is 256nm, the pore diameter variance is 1.2, and the specific surface area is 772m²g^-1The fluorescence quantum yield is 77%; the polystyrene high-fluorescence microsphere shows color change under a certain temperature condition, and specifically comprises the following steps: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red; the present color change further includes a fluorescent color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes; the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere in a normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red; when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow; after the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is recovered to deep red;

Example 11

(1) preparing polystyrene high-fluorescence microspheres;

(1.1) mixing styrene, 1-vinyl-7-Br-perylene imide derivative (prepared in example 4) and peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1:85, and the molar ratio of styrene to 1-vinyl-7-Br-perylene imide derivative is 6: 1;

(1.2) adding deionized water and an emulsion (sodium dodecyl sulfate) into the mixture 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: 80; (1.3) adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microsphere, wherein the mass ratio of the demulsifier to the styrene is 6: 80;

(2) preparing polystyrene microsphere/PET master batch: adding low-melting-point PET powder (with a melting point of 184 ℃) and polystyrene high-fluorescence microspheres into a mixer for mixing, and carrying out melt extrusion on the mixed components through a screw extruder to prepare polystyrene microsphere/PET master batch, wherein the rotating speed of the mixer is 59r/min, the mixing time is 34min, the temperature of the screw extruder is 247 ℃, the rotating speed is 304r/min, and the mass fraction of the polystyrene high-fluorescence microspheres in the polystyrene microsphere/PET master batch is 24%;

(3) preparing temperature reversible response PET fiber: performing skin-core composite spinning on two components, namely polystyrene microsphere/PET master batch and PET, specifically, spinning by taking PET as a core layer component and polystyrene microsphere/PET master batch as a skin layer component under a POY (polyester pre-oriented yarn) process to prepare temperature reversible response POY (polyester pre-oriented yarn) yarns, and then performing texturing on the temperature reversible response POY yarns under a DTY (draw texturing yarn) process to prepare temperature reversible response PET fibers, wherein the mass ratio of the skin layer to the core layer is 1: 2.2;

the parameters of the POY process are as follows: the temperature of the spinning box body is 265 ℃, the temperature of the side blowing is 41 ℃, the wind speed is 0.8m/s, the relative humidity is 61%, the speed of the first godet is 2648m/min, the speed of the second godet is 2648m/min, and the winding speed is 2648 m/min;

the DTY process comprises the following steps: feeding the temperature reversible response POY yarn into a first roller, and preparing the temperature reversible response PET fiber through a yarn guide porcelain I, a hot box, a yarn guide porcelain II, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot; the temperature of the hot box was 148 ℃.

Polystyrene high-fluorescence microspheres are dispersed in the skin layer of the finally prepared temperature reversible response PET fiber; the polystyrene high-fluorescence 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 is 280nm, the pore diameter variance is 1.4, and the specific surface area is 783m²g^-1The fluorescence quantum yield is 78%; the polystyrene high-fluorescence microsphere shows color change under a certain temperature condition, and specifically comprises the following steps: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red; the present color change further includes a fluorescent color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes; the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere in a normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red; when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow; recovering to normal temperatureAfter 1-2 min, recovering the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere, recovering the peak value to 645-655 nm, and recovering the fluorescence color of the polystyrene high-fluorescence microsphere to be deep red;

Example 12

(1) preparing polystyrene high-fluorescence microspheres;

(1.1) mixing styrene, 1-vinyl-7-Br-perylene imide derivative (prepared in example 5) and peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1:82, and the molar ratio of styrene to 1-vinyl-7-Br-perylene imide derivative is 6: 1;

(1.2) adding deionized water and an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, heating to 85 ℃ within 4 minutes, continuing for 2 hours, and stopping the reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 2.8: 80; (1.3) adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microspheres, wherein the mass ratio of the demulsifier to the styrene is 5.2: 80; (2) preparing polystyrene microsphere/PET master batch: adding low-melting-point PET powder (the melting point is 208 ℃) and polystyrene high-fluorescence microspheres into a mixer for mixing, and carrying out melt extrusion on the mixed components through a screw extruder to prepare polystyrene microsphere/PET master batch, wherein the rotating speed of the mixer is 64r/min, the mixing time is 31min, the temperature of the screw extruder is 226 ℃, the rotating speed is 313r/min, and the mass fraction of the polystyrene high-fluorescence microspheres in the polystyrene microsphere/PET master batch is 19%;

(3) preparing temperature reversible response PET fiber: performing skin-core composite spinning on two components, namely polystyrene microsphere/PET master batch and PET, specifically, spinning by taking PET as a core layer component and polystyrene microsphere/PET master batch as a skin layer component under a POY (polyester pre-oriented yarn) process to prepare temperature reversible response POY (polyester pre-oriented yarn) yarns, and then performing texturing on the temperature reversible response POY yarns under a DTY (draw texturing yarn) process to prepare temperature reversible response PET fibers, wherein the mass ratio of the skin layer to the core layer is 1: 2.5;

the parameters of the POY process are as follows: the temperature of the spinning box body is 280 ℃, the temperature of the side blowing is 25 ℃, the wind speed is 1.2m/s, the relative humidity is 70 percent, the speed of the first godet is 3313m/min, the speed of the second godet is 3313m/min, and the winding speed is 3313 m/min;

the DTY process comprises the following steps: feeding the temperature reversible response POY yarn into a first roller, and preparing the temperature reversible response PET fiber through a yarn guide porcelain I, a hot box, a yarn guide porcelain II, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot; the temperature of the hot box was 157 ℃.

Polystyrene high-fluorescence microspheres are dispersed in the skin layer of the finally prepared temperature reversible response PET fiber; the polystyrene high-fluorescence 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 is 323nm, the pore diameter variance is 0.9, and the specific surface area is 780m²g^-1The fluorescence quantum yield is 80%; the polystyrene high-fluorescence microsphere shows color change under a certain temperature condition, and specifically comprises the following steps: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red; the present color change further includes a fluorescent color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes; solid fluorescence of polystyrene high-fluorescence microsphere in normal temperature stateThe peak value of an emission peak in the spectrum is 645-655 nm; the fluorescence color of the microsphere is dark red; when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow; after the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is recovered to deep red;

Example 13

(1) preparing polystyrene high-fluorescence microspheres;

(1.1) mixing styrene, 1-vinyl-7-Br-perylene imide derivative (prepared in example 6) and peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1:80, and the molar ratio of styrene to 1-vinyl-7-Br-perylene imide derivative is 6: 1;

(1.2) adding deionized water and an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, heating to 88 ℃ within 4 minutes, continuing for 2 hours, and stopping the reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 3.5: 80; (1.3) adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microspheres, wherein the mass ratio of the demulsifier to the styrene is 6.9: 80;

(2) preparing polystyrene microsphere/PET master batch: adding low-melting-point PET powder (with a melting point of 218 ℃) and polystyrene high-fluorescence microspheres into a mixer for mixing, and carrying out melt extrusion on the mixed components through a screw extruder to prepare polystyrene microsphere/PET master batch, wherein the rotating speed of the mixer is 60r/min, the mixing time is 33min, the temperature of the screw extruder is 220 ℃, the rotating speed is 308r/min, and the mass fraction of the polystyrene high-fluorescence microspheres in the polystyrene microsphere/PET master batch is 17%;

(3) preparing temperature reversible response PET fiber: performing skin-core composite spinning on two components, namely polystyrene microsphere/PET master batch and PET, specifically, spinning by taking PET as a core layer component and polystyrene microsphere/PET master batch as a skin layer component under a POY (polyester pre-oriented yarn) process to obtain temperature reversible response POY (polyester pre-oriented yarn) yarns, and then performing texturing on the temperature reversible response POY yarns under a DTY (draw texturing yarn) process to obtain temperature reversible response PET fibers, wherein the mass ratio of the skin layer to the core layer is 1: 3.2;

the parameters of the POY process are as follows: the temperature of the spinning box body is 293 ℃, the temperature of the lateral blowing is 26 ℃, the wind speed is 1.5m/s, the relative humidity is 65%, the speed of the first godet is 3004m/min, the speed of the second godet is 3004m/min, and the winding speed is 3004 m/min;

Polystyrene high-fluorescence microspheres are dispersed in the skin layer of the finally prepared temperature reversible response PET fiber; the polystyrene high-fluorescence 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 is 365nm, the pore diameter variance is 1.2, and the specific surface area is 800m²g^-1The fluorescence quantum yield is 71%; the polystyrene high-fluorescence microsphere shows color change under a certain temperature condition, and specifically comprises the following steps: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red; the above-mentionedThe color change also includes fluorescence color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes; the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere in a normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red; when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow; after the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is recovered to deep red;

Example 14

(1) preparing polystyrene high-fluorescence microspheres;

(1.1) mixing styrene, 1-vinyl-7-Br-perylene imide derivative (prepared in example 3) and peroxide initiator (dibenzoyl peroxide) to obtain a mixture, wherein the mass ratio of dibenzoyl peroxide to styrene is 1:78, and the molar ratio of styrene to 1-vinyl-7-Br-perylene imide derivative is 6: 1;

(1.2) adding deionized water and an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, heating to 90 ℃ within 5 minutes, continuing for 2 hours, and stopping the reaction to obtain an emulsion, wherein the mass ratio of the emulsion to styrene is 3.8: 80; (1.3) adding a demulsifier (sodium chloride) into the emulsion under the stirring condition, stirring, condensing, filtering, washing with hot water, and drying to obtain the polystyrene high-fluorescence microspheres, wherein the mass ratio of the demulsifier to the styrene is 8: 80; (2) preparing polystyrene microsphere/PET master batch: adding low-melting-point PET powder (with a melting point of 220 ℃) and polystyrene high-fluorescence microspheres into a mixer for mixing, and carrying out melt extrusion on the mixed components through a screw extruder to prepare polystyrene microsphere/PET master batch, wherein the rotating speed of the mixer is 65r/min, the mixing time is 35min, the temperature of the screw extruder is 250 ℃, the rotating speed is 320r/min, and the mass fraction of the polystyrene high-fluorescence microspheres in the polystyrene microsphere/PET master batch is 25%;

(3) preparing temperature reversible response PET fiber: performing skin-core composite spinning on two components, namely polystyrene microsphere/PET master batch and PET, specifically, spinning by taking PET as a core layer component and polystyrene microsphere/PET master batch as a skin layer component under a POY (polyester pre-oriented yarn) process to prepare temperature reversible response POY (polyester pre-oriented yarn) yarns, and then performing texturing on the temperature reversible response POY yarns under a DTY (draw texturing yarn) process to prepare temperature reversible response PET fibers, wherein the mass ratio of the skin layer to the core layer is 1: 4;

the parameters of the POY process are as follows: the temperature of a spinning box body is 300 ℃, the temperature of lateral blowing is 50 ℃, the wind speed is 1.5m/s, the relative humidity is 95 percent, the speed of a first godet is 3500m/min, the speed of a second godet is 3500m/min, and the winding speed is 3500 m/min;

the DTY process comprises the following steps: feeding the temperature reversible response POY yarn into a first roller, and preparing the temperature reversible response PET fiber through a yarn guide porcelain I, a hot box, a yarn guide porcelain II, a false twister, the first roller, a netlike device, a third roller, an oil tanker, a winding roller and a coiled DTY yarn ingot; the temperature of the hot box was 180 ℃.

Polystyrene high-fluorescence microspheres are dispersed in the skin layer of the finally prepared temperature reversible response PET fiber; the polystyrene high-fluorescence 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 is 400nm, the pore diameter variance is 1.8, and the specific surface area is 750m²g^-1The fluorescence quantum yield is 65%; polystyrene high fluorescenceThe microsphere shows color change under a certain temperature condition, and specifically comprises the following components: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red; the present color change further includes a fluorescent color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes; the peak value of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere in a normal temperature state is 645-655 nm; the fluorescence color of the microsphere is dark red; when the ambient temperature is higher than 50-100 ℃, the blue shift of an emission peak in a solid fluorescence spectrum of the polystyrene high-fluorescence microsphere is 10-15 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is orange yellow; after the normal temperature is recovered for 1-2 min, the solid fluorescence spectrum emission peak of the polystyrene high-fluorescence microsphere is recovered, the peak value is recovered to 645-655 nm, and the fluorescence color of the polystyrene high-fluorescence microsphere is recovered to deep red;

Claims

1. A temperature reversible response PET fiber with low addition of functional materials is characterized in that: the PET fiber is prepared by sheath-core composite spinning and has reversible temperature response; polystyrene high-fluorescence microspheres are dispersed in the skin layer of the temperature reversible response PET fiber;

the polystyrene high-fluorescence 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;

2. The temperature reversible response PET fiber with low addition of functional materials according to claim 1, wherein the polystyrene high fluorescence microsphere shows color change under a certain temperature condition, specifically: when the ambient temperature is more than 50-100 ℃, the color of the polystyrene high-fluorescence microsphere is changed from deep red to orange yellow; and after the normal temperature is recovered for 1-2 min, the color of the polystyrene high-fluorescence microsphere is recovered to be deep red.

3. The temperature-reversible-response PET fiber with low addition of functional materials according to claim 2, characterized in that the color change further comprises a fluorescence color change, specifically: under the excitation of the wavelength of 440-460 nm, the peak value of the emission peak in the solid fluorescence spectrum of the polystyrene high-fluorescence microsphere changes and the fluorescence color of the polystyrene high-fluorescence microsphere changes:

4. The PET fiber with low addition of functional materials and reversible temperature response of claim 1, wherein the molecular formula of the 1-vinyl-7-Br-perylene imide derivative is as follows:

5. The PET fiber with low addition of functional materials and reversible temperature response of claim 1, wherein the polystyrene high-fluorescence microsphere has an average diameter of 150-400 nm, a pore size variance of 0.9-1.8, and a specific surface area of 750-800 m²g^-1The yield of the fluorescence quantum is 60-80%.

6. The method for preparing the temperature reversible response PET fiber with low addition of the functional material according to any one of claims 1 to 5, which is characterized in that: performing skin-core composite spinning on the polystyrene microsphere/PET master batch and the PET, specifically, firstly, taking the PET as a core layer component and the polystyrene microsphere/PET master batch as a skin layer component, spinning under a POY (polyester pre-oriented yarn) process to prepare a temperature reversible response POY (polyester pre-oriented yarn) filament, and then, texturing the temperature reversible response POY filament under a DTY (draw texturing yarn) process to prepare a temperature reversible response PET fiber;

7. The preparation method of the temperature reversible response PET fiber with the low addition amount of the functional material, according to claim 6, is characterized in that in the preparation of the polystyrene high-fluorescence microsphere, the mass ratio of the peroxide initiator to the styrene is 1: 75-85; the molar ratio of the styrene to the 1-vinyl-7-Br-perylene imide derivative is 5-6: 1; the peroxide initiator is dibenzoyl peroxide; the rapid heating is carried out within 5 minutes, T is 75-90 ℃, and the period of time is 2-6 hours; the demulsifier is sodium chloride, and the mass ratio of the demulsifier to styrene is 1.2-8: 80; the emulsion is sodium dodecyl sulfate, and the mass ratio of the emulsion to styrene is 0.5-3: 80.

8. The preparation method of the temperature reversible response PET fiber with the low addition amount of the functional material, according to claim 6, is characterized in that the mass ratio of the skin layer to the core layer of the temperature reversible response PET fiber is 1: 0.25-4; in the polystyrene microsphere/PET master batch, the mass fraction of the polystyrene high-fluorescence microsphere is 15-25%; the melting point of the low-melting-point PET powder is 180-220 ℃.

9. The preparation method of the temperature reversible response PET fiber with low addition of the functional material, according to claim 6, is characterized in that in the preparation of the polystyrene microsphere/PET master batch, the rotating speed of a mixer is 55-65 r/min, the mixing time is 30-40 min, the temperature of a screw extruder is 220-250 ℃, and the rotating speed is 300-320 r/min;

the parameters of the POY process are as follows: the temperature of a spinning box body is 250-300 ℃, the temperature of cross air blowing is 10-50 ℃, the air speed is 0.1-1.5 m/s, the relative humidity is 55-95%, the speed of a first yarn guide disc is 2500-3500 m/min, the speed of a second yarn guide disc is 2500-3500 m/min, and the winding speed is 2500-3500 m/min;