CN111893595B

CN111893595B - Polyester fiber with fluorescent and flame-retardant functions and preparation method thereof

Info

Publication number: CN111893595B
Application number: CN202010656722.8A
Authority: CN
Inventors: 孙小国; 邓锋; 孙宾; 孙正清; 沈静; 潘月月
Original assignee: Shanghai Huiyi New Material Technology Co ltd; Donghua University
Current assignee: Shanghai Huiyi New Material Technology Co ltd; Donghua University
Priority date: 2020-07-09
Filing date: 2020-07-09
Publication date: 2022-09-23
Anticipated expiration: 2040-07-09
Also published as: CN111893595A

Abstract

The invention relates to a polyester fiber with fluorescence and flame-retardant functions and a preparation method thereof, the method comprises the steps of firstly adding fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing, carrying out melt extrusion to obtain functional master batches, and then carrying out melt blending spinning by taking the mixture of the functional master batches and PET slices as raw materials to obtain the fluorescent flame-retardant polyester fiber, wherein the polyacrylic acid microspheres are prepared by taking 1, 7-vinyl-perylene imide derivatives (perylene imide of which gulf site (1,7 site) has a substituent of a vinyl group and imide site has a large-volume substituent) as a cross-linking agent; the fluorescence quantum yield of the fluorescent flame-retardant polyester fiber is 60-80%, and a characteristic fluorescence emission peak of a 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 30-35, and the vertical burning grade is UL 94V-0 grade.

Description

Polyester fiber with fluorescent and flame-retardant functions and preparation method thereof

Technical Field

The invention belongs to the technical field of polyester fibers, and relates to a polyester fiber with fluorescence and flame retardant functions and a preparation method thereof.

Background

The polyester fiber has the characteristics of high strength, good elasticity, strong wrinkle resistance, good wear resistance, excellent heat resistance and the like. Therefore, the textile is an ideal textile material for both civil use and industry. Polyester fibers are the varieties with the largest output and the widest application in synthetic fibers at present, and are widely applied to the fields of clothes, industry, Jiatong transportation, decorative materials and the like due to good mechanical properties and tensile properties of the polyester fibers. However, with the expansion of the application field, in some special fields, such as military affairs, aviation, transportation, entertainment places, hospitals and other decoration materials and fire-fighting facilities, certain requirements on flame retardance and garment visibility are required. In the fields of petroleum, mining industry, fire rescue and the like, high-visibility fabrics are also needed for being found in severe environments for the first time, and since the workers in the industries are also easily threatened by flammable and explosive dangerous goods, the fabrics applied to the fields also fully consider the protective properties such as flame retardance and the like.

Currently, PET flame-retardant products are competitively developed all over the world, but the existing flame-retardant PET has the following problems in practical application: some flame retardant PET produces smoke and toxic and harmful gases when burning. Some flame-retardant PET has excellent flame-retardant and smoke-inhibiting functions, but the mechanical properties of the material are reduced too much, and the fiber is difficult to form, so that the practical use requirements are difficult to meet.

The fabric made of the fluorescent fibers is called as high-visibility warning fabric and is mainly used for high-visibility warning clothes. With the development of society, traffic accidents become one of the most common hazards in the current society, and the effective development of work for preventing and reducing traffic accidents becomes an urgent task in the current society. Statistically, 40% of traffic accidents that cause death occur at night because 90% of drivers visually obtain driving information. Therefore, for some special working environments, the danger faced by workers tends to be complicated and diversified, and particularly, the working environment of special workers such as fire fighting personnel, traffic police personnel, airport runway workers and the like is often dark at night, cold or wind and snow, and the workers need to wear highly visible clothes. Meanwhile, workers also need to prevent fire and heat damages in the environment, so that the required protective fabric has multiple functions of high visibility, high temperature resistance, flame retardance and the like.

Patent CN109208114A relates to a flame-retardant antibacterial PET fiber and a slice spinning preparation method thereof, wherein a PET slice and a metal modified hyperbranched polymer are subjected to melt blending to prepare a functional masterbatch, and the functional masterbatch and the PET slice are uniformly mixed and then subjected to melt spinning to prepare the flame-retardant antibacterial PET fiber. The prepared product is uniformly dispersed with metal modified hyperbranched polymer, the metal modified hyperbranched polymer is a network polymer formed by crosslinking hyperbranched polymer with carboxyl at the end group and metal ions, and the metal modified hyperbranched polymer has the characteristics of insolubility and infusibility, is insoluble in most organic solvents below 80 ℃, and is infusible within the range from room temperature to T (T is more than or equal to 370 ℃); the cross-linking is realized by connecting oxygen atoms on double bonds in the hyperbranched polymer molecules with carboxyl at the end groups with metal ions through coordination bonds and connecting acid radical ions at the tail ends of the hyperbranched polymer molecules with carboxyl at the end groups with the metal ions through ionic bonds. The content of the metal modified hyperbranched polymer is further increased, although the limit oxygen index of the fiber is further improved, the improvement range is limited, and the cost performance is not good; the content of the metal modified hyperbranched polymer is too small, so that the limit oxygen index of the fiber is difficult to ensure. Patent CN108754670A provides a fluorescent flame-retardant fiber and a preparation method thereof, the fiber includes a skin layer and a core layer, the skin layer is a composition of fluorescent color master batch and flame-retardant polyester, and the core layer is flame-retardant polyester. The fiber combines the fluorescent material and the flame-retardant material, so that permanent fluorescent and flame-retardant fibers can be formed, and the durability of the visible flame-retardant warning garment is further improved. The double-extruder spinning adopts two sets of extrusion equipment, one set of extrusion equipment is responsible for producing the skin layer, the other set of extrusion equipment is responsible for producing the core layer, the fiber is produced by a skin-core spinning process, the preparation method is complex, and the equipment requirement is high.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a polyester fiber with fluorescent and flame-retardant functions and a preparation method thereof.

The invention aims to provide a polyester fiber with both fluorescent and flame-retardant functions, namely a fluorescent flame-retardant polyester fiber prepared by melt blending spinning, namely a polyester fiber with both fluorescent and flame-retardant functions; fluorescent flame-retardant microspheres made of polyacrylic acid microspheres are dispersed in the fluorescent flame-retardant polyester fibers;

the invention also aims to provide a preparation method of the polyester fiber with the fluorescence and flame retardant functions, which comprises the steps of adding the fluorescent flame retardant microspheres and the PET resin powder into a high-speed mixer, mixing, performing melt extrusion to obtain functional master batches, and performing melt blending spinning by using the mixture of the functional master batches and the PET slices as raw materials to obtain the fluorescent flame retardant polyester fiber with the fluorescence and flame retardant functions.

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

a polyester fiber with both fluorescent and flame-retardant functions mainly comprises a polyester matrix and fluorescent flame-retardant microspheres dispersed in the polyester matrix;

the fluorescent flame-retardant microspheres are polyacrylic microspheres loaded with zinc acetate dihydrate and [ (6-oxy (6H) -dibenzo- (c, e) (1,2) -oxaphosphorin-6-ketone) methyl ] -succinic acid (DDP);

the polyacrylic acid microspheres are polyacrylic acid microspheres which take 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents;

the 1, 7-vinyl-perylene bisimide derivative is perylene bisimide with substituent groups with ethylene groups at gulf positions (1,7 positions) and bulky substituent groups at imide positions.

As a preferred technical scheme:

the polyester fiber with the functions of fluorescence and flame retardance is characterized in that the bulky substituent is sesqui-cage siloxane 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 an imide structure;

the substituent of the ethylene group is an alkyl chain with an ethylene group at the end group, and the alkyl chain is an alkyl chain with less than six carbons.

According to the polyester fiber with the fluorescent and flame-retardant functions, in the polyacrylic acid microsphere, the molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit is 14-21.5: 125, and if the addition amount of the 1, 7-vinyl-perylene imide derivative is too small, the color of the microsphere is too light, the color is not obvious, and the too large spinnability is poor.

According to the polyester fiber with the fluorescent and flame-retardant functions, the fluorescent quantum yield of the polyacrylic acid microspheres is 95-99%, and under excitation of the wavelength of 440-460 nm, a characteristic fluorescent emission peak of a 630-645 nm 1, 7-vinyl-perylene imide derivative is generated, and the color is orange yellow; the average diameter of the polyacrylic acid microspheres is 150-300 nm, the average pore diameter is 10-30 nm, and the porosity is 35-55%; the surface is rough and porous, the folding degree is higher, the specific surface area is large, and the reactive carboxyl groups are exposed; the phosphorus content in the fluorescent flame-retardant microspheres is 3.75-25 wt%, and the zinc content is 1.25-15 wt%.

The fluorescent flame-retardant polyester fiber has the fluorescent and flame-retardant functions, the fineness of the fluorescent flame-retardant polyester fiber is 3.2-4 dtex, the breaking strength is 3-4.5 cN/dtex, and the elongation at break is 13.2-17.4%; the fluorescence quantum yield is 60-80%, and under excitation of a wavelength of 440-460 nm, a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated, and the color is orange yellow; the flame retardant property is as follows: the limiting oxygen index LOI value is 30-35, and the vertical burning grade is UL 94V-0 grade.

The method for testing the limiting oxygen index LOI value comprises the following steps: with reference to GB/T5454-1997, the specimen size is 150mm × 58mm, 15 blocks are provided for each warp and weft, the specimen is clamped on a specimen holder perpendicular to the combustion cylinder, the upper end of the specimen is ignited in the upward flowing oxygen-nitrogen gas flow, the combustion characteristic is observed, and the limit oxygen index value is evaluated by comparing the after-flame time or the damage length with the specified limit value. The samples were conditioned prior to testing.

The test method of the vertical burning grade comprises the following steps: with reference to GB/T5455-1997, the test specimens have dimensions of 300mm x 80mm, 5 blocks each for warp and weft, are ignited by placing them under a specified burner, are ignited for 12s in a specified combustion chamber by a specified ignition source, and the after-flame time and the smoldering time of the test specimens are measured after the ignition source is removed. After smoldering combustion is stopped, the damage length is measured according to a specified method, and the vertical combustion grade is evaluated. The samples were conditioned prior to testing.

The preparation method of the polyester fiber with the fluorescence and flame-retardant functions comprises the steps of adding the fluorescent flame-retardant microspheres and the PET resin powder into a high-speed mixer, mixing, performing melt extrusion to obtain the functional master batches, and performing melt blending spinning by taking the mixture of the functional master batches and the PET slices as raw materials to obtain the fluorescent flame-retardant polyester fiber, namely the polyester fiber with the fluorescence and flame-retardant functions;

the preparation method of the fluorescent flame-retardant microspheres comprises the following steps:

(1) mixing an emulsifier and deionized water at a temperature T1 to form a system I;

(2) firstly, dissolving methyl acrylate and 1, 7-vinyl-perylene bisimide derivatives in an organic solvent, adding the mixture into a system I, and mixing at a temperature of T2 to obtain a system II;

(3) firstly, stirring a system II for a certain time, and then adding potassium persulfate into the system II to initiate polymerization to obtain a polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature (23 +/-2 ℃), filtering, washing and drying to obtain polyacrylate microspheres;

(4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, heating, refluxing, cooling, filtering, and drying (washing with water for several times, washing with dilute hydrochloric acid for one time, and washing with water for several times before drying) to obtain polyacrylic microspheres (solid powder);

(5) dispersing polyacrylic acid microspheres in an organic solvent to prepare a suspension;

(6) adding zinc acetate dihydrate and DDP ([ (6-oxo-6H-dibenzo [ c, e ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid) into the suspension, uniformly dissolving under the stirring condition (stirring is mechanical stirring or magnetic stirring, the stirring speed is 200-500 rpm, the stirring time is 0.5-1H, ultrasonic oscillation is carried out simultaneously, the power is 600-1200W) at room temperature (23 +/-2 ℃), dripping deionized water at a certain speed, and separating out a white precipitate to obtain a mixed solution;

(7) and filtering, washing (washing by using a large amount of deionized water, and replacing the water in the mixture by using absolute ethyl alcohol) and drying the mixture to obtain the fluorescent flame-retardant microspheres.

According to the preparation method of the polyester fiber with the fluorescent and flame-retardant functions, the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1: 1.85-5.25; and during melt blending spinning, the mass ratio of the functional master batch to the PET chips is 1: 11.5-13.3.

According to the preparation method of the polyester fiber with the fluorescent and flame-retardant functions, the melt extrusion temperature is 220-250 ℃, and the pressure is 4-6 MPa; the melt blending spinning process comprises the following steps: the spinning temperature is 270-295 ℃; the temperature of the cross air blow is 28-30 ℃, and the air speed of the cross air blow is 0.3-0.5 m/s; the winding spinning speed is 3500-4000 m/min; the drafting multiplying power is 3.0-4.0;

the intrinsic viscosity of the PET slices is 0.6-0.9 dl/g;

the mixing time of the high-speed mixer is 30-40 min; before mixing in the high-speed mixer, drying the fluorescent flame-retardant microspheres and the PET at the temperature of 60-80 ℃ for 30-40 min.

According to the preparation method of the polyester fiber with the fluorescent and flame-retardant functions, the emulsifier is potassium laurate, sodium dodecyl sulfate or dioctyl sodium sulfosuccinate; the organic solvent is toluene or xylene.

According to the preparation method of the polyester fiber with the fluorescent and flame-retardant functions, in the step (1), T1 is 35-55 ℃, and the mixing time is 3-8 min;

in the system II in the step (2), the content of the emulsifier is 0.4-0.7 wt%, the content of the methyl acrylate is 4-6 wt%, the content of the 1, 7-vinyl-perylene imide derivative is 9-15 wt%, and the content of the organic solvent is 6-10 wt%; t2 is 75-95 ℃, the stirring speed is 300-500 r/min, and the stirring time is 15-35 min;

in the step (3), the addition amount of the potassium persulfate is 1-5 wt% of the polyacrylate dispersion liquid; the polymerization time is 4-8 h, and the polymerization temperature is 75-95 ℃; the drying temperature is 90-140 ℃;

the concentration of the sodium hydroxide ethanol solution in the step (4) is 1-2 mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1-3; the heating reflux time is 9-11 h, and the drying temperature is 90-110 ℃;

in the step (5), the organic solvent is DMF, chloroform or acetone, and the mass fraction of the polyacrylic acid microspheres in the suspension is 5-20%;

in the step (6), the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, and the mass ratio of the polyacrylic acid microspheres to the DDP is 1: 1-1.5; the certain speed is 0.5-1 drop/s;

in the step (7), drying is carried out under vacuum condition, wherein the vacuum degree is-0.1 MPa, the drying time is 8-12 h, and the drying temperature is 40 ℃.

The principle of the invention is as follows:

the 1, 7-vinyl-perylene imide derivative has fluorescence property, and the 1, 7-vinyl-perylene imide derivative with a bulky imide site substituent group can ensure that the 1, 7-vinyl-perylene imide derivative has great steric hindrance when being aggregated through pi-pi interaction, and can more easily exist in a system in a monomolecular state under the condition of a solvent. Finally, the 1, 7-vinyl-perylene imide derivative can be used as a cross-linking agent to enter the polyacrylate microsphere in a monomolecular state. The 1, 7-vinyl-perylene imide derivative is also a fluorescent molecule, and the 1, 7-vinyl-perylene imide derivative generates fluorescence quenching when being aggregated through pi-pi interaction, so that the fluorescence quantum yield is reduced, and the related fluorescence performance is reduced. According to the invention, the 1, 7-vinyl-perylene bisimide derivative enters a system in a monomolecular state, so that the aggregation of the derivative is effectively avoided, the occurrence of fluorescence quenching is avoided, and the good fluorescence property of the 1, 7-vinyl-perylene bisimide derivative is maintained; DDP is a monomer of the copolymerized polyester flame-retardant resin, can effectively play a flame-retardant role by being introduced into a PET molecular chain through copolymerization, but can generate adverse effects on the regularity, crystallization performance and stability of PET;

the invention adopts 1, 7-vinyl-perylene imide derivatives as cross-linking agents to prepare polyacrylate microspheres, and hydrolyzes the polyacrylate microspheres into polyacrylic microspheres, so that the polyacrylic microspheres have porous structures, large specific surface areas and multiple reactive carboxyl groups are exposed. Then, loading DDP on polyacrylic acid microspheres to prepare fluorescent flame-retardant microspheres; the loading mechanism of DDP is: zn ²⁺ The compound can generate chelation with carboxyl in DDP molecules and carboxyl on polyacrylic acid microspheres to fix the DDP molecules in the microspheres chemically; at the same time, Zn ²⁺ Or chelating with a plurality of DDP molecules to ensure that the DDP molecules are insoluble and separated out in the microspheres; p ═ O and C ═ O and Zn in DDP ²⁺ The coordination of (a) will also enhance the interaction; the DDP, the polyacrylic acid and the zinc acetate dihydrate in the fluorescent flame-retardant microsphere are fixed together under the action, and the carboxyl group in the polyacrylic acid microsphere is far away from the 1, 7-vinyl-perylene bisimide derivative, so that the carboxylic acid group in the microsphere can participate in chelation without generating great influence on the fluorescence property. So that the microspheres have flame retardant effect and high flame retardant performance under the condition of small addition amount (using relatively small phosphorus content). The invention further blends and granulates the fluorescent flame-retardant microspheres and the polyester, and the polyester fiber with the fluorescent and flame-retardant functions is spun by a melt spinning method.

Has the advantages that:

(1) the polyester fiber with the fluorescent and flame-retardant functions can meet the production requirements of fabrics with the fluorescent and flame-retardant properties in life and production, and can ensure that the polyester fiber has better flame-retardant property under the condition of lower phosphorus content;

(2) according to the preparation method of the polyester fiber with the fluorescence and flame retardant functions, the polyester fiber with the fluorescence and flame retardant functions is prepared mainly by adding the functional microspheres, the modification of a matrix polymer structure is not needed, the preparation method is simple, and the equipment requirement is low.

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 can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.

Example 1

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

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

(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.

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 show 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

(0.50mmol) 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 spin-drying the extracted trichloromethane solution to obtain a crude product of the 1, 7-vinyl-perylene bisimide derivative, and performing column chromatography to obtain a product of the 1, 7-vinyl-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 1 h. Is then added

(4.5mmol), R is isobutyl, 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.

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. Anhydrous potassium carbonate (55.4mg,0.40mmol), 18-crown-6-ether (105.73mg,0.40mmol) were then added to the system and pipetted

(0.50mmol) 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.

Example 3

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. Followed by the addition of 2-ethylhexylamine

(4.5mmol), glacial acetic acid (16mL,140 mmol). The temperature is raised to 85 ℃ under the protection of nitrogen, and the reaction is continued for 7 h. 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.

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

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. 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, 7-vinyl-perylene bisimide derivative, and performing column chromatography to obtain a product of the 1, 7-vinyl-perylene bisimide derivative.

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

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

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 adding anhydrous carbonic acid into the systemPotassium (55.4mg,0.40mmol), 18-crown-6-ether (105.73mg,0.40mmol) and pipetted with a pipette

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

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 crude product of the 1, 7-vinyl-perylene bisimide derivative, and performing column chromatography to obtain a product of the 1, 7-vinyl-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 dissolved and stirred at 25 ℃ for 1 h. Followed by addition of

(4.5mmol), R is isooctyl, 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. Suction filtration to obtainAnd (4) obtaining red solid, drying for 24h in vacuum, and performing column chromatography at 85 ℃ to obtain 1, 7-Br-PDI-X.

Example 7

A preparation method of polyester fiber with fluorescence and flame retardant functions comprises the following steps:

(1) preparing fluorescent flame-retardant microspheres:

(1.1) mixing potassium laurate and deionized water at a temperature T1(35 ℃) to form a system I;

(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene bisimide derivative (prepared in example 1) in toluene, adding the mixture into the system I, and mixing at the temperature of T2(75 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 4 wt%, the content of 1, 7-vinyl-perylene imide derivatives is 13.6 wt%, the content of toluene is 10 wt%, and the content of potassium laurate is 0.4 wt%;

(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 1 wt% of the polyacrylate dispersion liquid; the polymerization time is 4h, and the polymerization temperature is 75 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 1mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1; the heating reflux time is 9h, and the drying temperature is 90 ℃;

the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 14: 125; the average diameter of the polyacrylic acid microspheres is 150nm, the average pore diameter is 10nm, and the porosity is 35%; the fluorescence quantum yield of the polyacrylic acid microspheres is 95%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;

(1.5) dispersing polyacrylic acid microspheres in DMF to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 5%;

(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.2 drop/s to obtain a mixed solution; the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1, and the adding amount of the deionized water is 1 time of the volume of the polyacrylic acid microspheres;

(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 8h, and the drying temperature is 40 ℃;

the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;

(2) preparing functional master batches:

adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing and preparing functional master batches through melt extrusion; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1:1.85, the mixing time of a high-speed mixer is 30min, the melt extrusion temperature is 220 ℃, and the pressure is 4 MPa;

(3) preparing polyester fiber with fluorescence and flame retardant functions:

the mixture of the functional master batch and the PET slices with the intrinsic viscosity of 0.6dl/g is used as a raw material to carry out melt blending spinning to prepare the fluorescent flame-retardant polyester fiber, namely the polyester fiber with both fluorescent and flame-retardant functions; wherein the mass ratio of the functional master batch to the PET slices is 1: 11.5;

the melt blending spinning process comprises the following steps: the spinning temperature is 270 ℃; the temperature of the cross air blow is 28 ℃, and the air speed of the cross air blow is 0.3 m/s; the winding spinning speed is 3500 m/min; the draft magnification was 3.0.

The fineness of the finally prepared polyester fiber with the functions of fluorescence and flame retardance is 3.2dtex, the breaking strength is 3cN/dtex, and the elongation at break is 17.4%; the fluorescence quantum yield is 60%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 30, and the vertical burning grade is UL 94V-0 grade.

Example 8

(1) preparing fluorescent flame-retardant microspheres:

(1.1) mixing potassium laurate and deionized water at a temperature of T1(48 ℃) to form a system I;

(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene imide derivative (prepared in example 4) in xylene, adding the mixture into the system I, and mixing at a temperature of T2(84 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 5 wt%, the content of 1, 7-vinyl-perylene imide derivative is 14.6 wt%, the content of xylene is 9 wt%, and the content of potassium laurate is 0.4 wt%;

(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 5h, and the polymerization temperature is 76 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 3; the heating reflux time is 11h, and the drying temperature is 98 ℃;

the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 16: 125; the average diameter of the polyacrylic acid microspheres is 207nm, the average pore diameter is 27nm, and the porosity is 50%; the fluorescence quantum yield of the polyacrylic acid microspheres is 98%, and characteristic fluorescence emission peaks of 630-645 nm 1, 7-vinyl-perylene imide derivatives are generated under excitation of a wavelength of 440-460 nm;

(1.5) dispersing polyacrylic acid microspheres in DMF to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 7%;

(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.1 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.2, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;

(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 9h, and the drying temperature is 40 ℃;

(2) preparing functional master batches:

adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing and preparing functional master batches through melt extrusion; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1:1.98, the mixing time of a high-speed mixer is 38min, the temperature of melt extrusion is 232 ℃, and the pressure is 6 MPa;

(3) preparing polyester fiber with fluorescence and flame retardant functions:

the mixture of the functional master batch and the PET slices with the intrinsic viscosity of 0.6dl/g is used as a raw material to carry out melt blending spinning to prepare the fluorescent flame-retardant polyester fiber, namely the polyester fiber with both fluorescent and flame-retardant functions; wherein the mass ratio of the functional master batch to the PET slices is 1: 11.8;

the melt blending spinning process comprises the following steps: the spinning temperature is 270 ℃; the temperature of the cross air blow is 28 ℃, and the air speed of the cross air blow is 0.5 m/s; the winding spinning speed is 3632 m/min; the draw ratio was 3.0.

The fineness of the finally prepared polyester fiber with the functions of fluorescence and flame retardance is 3.5dtex, the breaking strength is 3.2cN/dtex, and the elongation at break is 17.2%; the yield of the fluorescence quantum is 70%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 34, and the vertical burning grade is UL 94V-0 grade.

Example 9

(1) preparing fluorescent flame-retardant microspheres:

(1.1) mixing potassium laurate and deionized water at a temperature of T1(40 ℃) to form a system I;

(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene imide derivative (prepared in example 2) in toluene, adding the obtained solution into the system I, and mixing the obtained mixture at a temperature of T2(80 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 4 wt%, the content of 1, 7-vinyl-perylene imide derivatives is 12.5 wt%, the content of toluene is 9 wt%, and the content of potassium laurate is 0.5 wt%;

(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 1 wt% of the polyacrylate dispersion liquid; the polymerization time is 4h, and the polymerization temperature is 80 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 3; the heating reflux time is 10h, and the drying temperature is 96 ℃;

the prepared polyacrylic acid microspheres are polyacrylic acid microspheres taking 1, 7-vinyl-perylene imide derivatives as a cross-linking agent, wherein the molar ratio of the 1, 7-vinyl-perylene imide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 20: 125; the average diameter of the polyacrylic acid microspheres is 235nm, the average pore diameter is 19nm, and the porosity is 53%; the fluorescence quantum yield of the polyacrylic acid microspheres is 99%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;

(1.5) dispersing polyacrylic acid microspheres in chloroform to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 17%;

(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.5 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.5, and the adding amount of the deionized water is 1.1 times of the volume of the polyacrylic acid microspheres;

(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 10h, and the drying temperature is 40 ℃;

(2) preparing functional master batches:

adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing and preparing functional master batches through melt extrusion; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1:2.3, the mixing time of a high-speed mixer is 34min, the melt extrusion temperature is 220 ℃, and the pressure is 4 MPa;

(3) preparing polyester fiber with fluorescence and flame retardant functions:

the mixture of the functional master batch and the PET slices with the intrinsic viscosity of 0.8dl/g is used as a raw material to carry out melt blending spinning to prepare the fluorescent flame-retardant polyester fiber, namely the polyester fiber with both fluorescent and flame-retardant functions; wherein the mass ratio of the functional master batch to the PET slices is 1: 11.9;

the melt blending spinning process comprises the following steps: the spinning temperature is 286 ℃; the temperature of the cross air blow is 28 ℃, and the air speed of the cross air blow is 0.5 m/s; the winding spinning speed is 3697 m/min; the draw ratio was 3.5.

The fineness of the finally prepared polyester fiber with the fluorescent and flame-retardant functions is 4dtex, the breaking strength is 3.3cN/dtex, and the elongation at break is 16.6%; the fluorescence quantum yield is 63%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 31, and the vertical burning grade is UL 94V-0 grade.

Example 10

A preparation method of polyester fiber with fluorescent and flame-retardant functions comprises the following steps:

(1) preparing fluorescent flame-retardant microspheres:

(1.1) mixing sodium lauryl sulfate and deionized water at a temperature T1(39 ℃) to form system I;

(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene bisimide derivative (prepared in example 6) in toluene, adding the mixture into the system I, and mixing at the temperature of T2(93 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 5 wt%, the content of 1, 7-vinyl-perylene imide derivative is 14.5 wt%, the content of toluene is 10 wt%, and the content of sodium dodecyl sulfate is 0.5 wt%;

(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 5h, and the polymerization temperature is 88 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1; the heating reflux time is 10h, and the drying temperature is 100 ℃;

the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 21.5: 125; the average diameter of the polyacrylic acid microsphere is 201nm, the average pore diameter is 21nm, and the porosity is 48%; the fluorescence quantum yield of the polyacrylic acid microspheres is 99%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;

(1.5) dispersing polyacrylic acid microspheres in acetone to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 5%;

(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.5 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.3, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;

(2) preparing functional master batches:

adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing and preparing functional master batches through melt extrusion; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1:4.54, the mixing time of a high-speed mixer is 30min, the temperature of melt extrusion is 239 ℃, and the pressure is 5 MPa;

(3) preparing polyester fiber with fluorescence and flame retardant functions:

the mixture of the functional master batch and the PET slices with the intrinsic viscosity of 0.9dl/g is used as a raw material to carry out melt blending spinning to prepare the fluorescent flame-retardant polyester fiber, namely the polyester fiber with both fluorescent and flame-retardant functions; wherein the mass ratio of the functional master batch to the PET slices is 1: 12;

the melt blending spinning process comprises the following steps: the spinning temperature is 286 ℃; the temperature of the cross air blow is 29 ℃, and the air speed of the cross air blow is 0.5 m/s; the winding spinning speed is 3961 m/min; the draft magnification was 3.0.

The fineness of the finally prepared polyester fiber with the fluorescent and flame-retardant functions is 4dtex, the breaking strength is 3.5cN/dtex, and the elongation at break is 16.2%; the fluorescence quantum yield is 72%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 31, and the vertical burning grade is UL 94V-0 grade.

Example 11

(1) preparing fluorescent flame-retardant microspheres:

(1.1) mixing sodium lauryl sulfate and deionized water at a temperature T1(55 ℃) to form system I;

(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene bisimide derivative (prepared in example 3) in toluene, adding the mixture into the system I, and mixing at the temperature of T2(93 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 6 wt%, the content of 1, 7-vinyl-perylene imide derivatives is 10.4 wt%, the content of toluene is 8 wt%, and the content of sodium dodecyl sulfate is 0.6 wt%;

(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 8h, and the polymerization temperature is 94 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1; the heating reflux time is 10h, and the drying temperature is 101 ℃;

the prepared polyacrylic acid microspheres are polyacrylic acid microspheres taking 1, 7-vinyl-perylene imide derivatives as a cross-linking agent, wherein the molar ratio of the 1, 7-vinyl-perylene imide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 14.5: 125; the average diameter of the polyacrylic acid microspheres is 290nm, the average pore diameter is 17nm, and the porosity is 55%; the fluorescence quantum yield of the polyacrylic acid microspheres is 98%, and characteristic fluorescence emission peaks of 630-645 nm 1, 7-vinyl-perylene imide derivatives are generated under excitation of a wavelength of 440-460 nm;

(1.5) dispersing polyacrylic acid microspheres in chloroform to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 7%;

(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 1 drop/s to obtain a mixed solution; the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.2, and the adding amount of the deionized water is 1.1 times of the volume of the polyacrylic acid microspheres;

(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 11h, and the drying temperature is 40 ℃;

(2) preparing functional master batches:

adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing, and performing melt extrusion to obtain functional master batches; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1:5.25, the mixing time of a high-speed mixer is 40min, the temperature of melt extrusion is 239 ℃, and the pressure is 4 MPa;

(3) preparing polyester fiber with fluorescence and flame retardant functions:

the mixture of the functional master batch and the PET slices with the intrinsic viscosity of 0.6dl/g is used as a raw material to carry out melt blending spinning to prepare the fluorescent flame-retardant polyester fiber, namely the polyester fiber with both fluorescent and flame-retardant functions; wherein the mass ratio of the functional master batch to the PET slices is 1: 12.5;

the melt blending spinning process comprises the following steps: the spinning temperature is 284 ℃; the temperature of the cross air blow is 30 ℃, and the air speed of the cross air blow is 0.5 m/s; the winding spinning speed is 3610 m/min; the draft magnification was 4.0.

The fineness of the finally prepared polyester fiber with the fluorescent and flame-retardant functions is 4dtex, the breaking strength is 3.8cN/dtex, and the elongation at break is 15.8%; the yield of the fluorescence quantum is 75%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 33, and the vertical burning grade is UL 94V-0 grade.

Example 12

(1) preparing fluorescent flame-retardant microspheres:

(1.1) mixing dioctyl sodium sulfosuccinate and deionized water at a temperature T1(38 ℃) to form a system I;

(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene imide derivative (prepared in example 2) in toluene, adding the obtained solution into the system I, and mixing the obtained mixture at a temperature of T2(94 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 6 wt%, the content of 1, 7-vinyl-perylene imide derivatives is 11.4 wt%, the content of toluene is 7 wt%, and the content of dioctyl sodium sulfosuccinate is 0.6 wt%;

(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 1 wt% of the polyacrylate dispersion liquid; the polymerization time is 7h, and the polymerization temperature is 84 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 1mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1; the heating reflux time is 11h, and the drying temperature is 99 ℃;

the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 14.3: 125; the average diameter of the polyacrylic acid microsphere is 288nm, the average pore diameter is 25nm, and the porosity is 47%; the fluorescence quantum yield of the polyacrylic acid microspheres is 97%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;

(1.5) dispersing polyacrylic acid microspheres in acetone to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 18%;

(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 1 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;

(2) preparing functional master batches:

adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing and preparing functional master batches through melt extrusion; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1:5, the mixing time of a high-speed mixer is 37min, the temperature of melt extrusion is 237 ℃, and the pressure is 6 MPa;

(3) preparing polyester fiber with fluorescence and flame retardant functions:

the mixture of the functional master batch and the PET slices with the intrinsic viscosity of 0.6dl/g is used as a raw material to carry out melt blending spinning to prepare the fluorescent flame-retardant polyester fiber, namely the polyester fiber with both fluorescent and flame-retardant functions; wherein the mass ratio of the functional master batch to the PET slices is 1: 13.2;

the melt blending spinning process comprises the following steps: the spinning temperature is 287 ℃; the temperature of the cross air blow is 30 ℃, and the air speed of the cross air blow is 0.4 m/s; the winding and spinning speed is 3987 m/min; the draw ratio was 4.0.

The fineness of the finally prepared polyester fiber with the functions of fluorescence and flame retardance is 3.5dtex, the breaking strength is 4cN/dtex, and the elongation at break is 15.4%; the fluorescence quantum yield is 72%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under the excitation of the wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 30, and the vertical burning grade is UL 94V-0 grade.

Example 13

(1) preparing fluorescent flame-retardant microspheres:

(1.1) mixing dioctyl sodium sulfosuccinate and deionized water at a temperature T1(36 ℃) to form a system I;

(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene imide derivative (prepared in example 5) in xylene, adding the mixture into the system I, and mixing at the temperature of T2(92 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 5 wt%, the content of 1, 7-vinyl-perylene imide derivative is 15 wt%, the content of xylene is 6 wt%, and the content of dioctyl sodium sulfosuccinate is 0.7 wt%;

(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 5h, and the polymerization temperature is 92 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 1mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 3; the heating reflux time is 11h, and the drying temperature is 101 ℃;

the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 15: 125; the average diameter of the polyacrylic acid microsphere is 290nm, the average pore diameter is 19nm, and the porosity is 50%; the fluorescence quantum yield of the polyacrylic acid microspheres is 99%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;

(1.5) dispersing polyacrylic acid microspheres in DMF to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 17%;

(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.5 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.2, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;

(2) preparing functional master batches:

adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing and preparing functional master batches through melt extrusion; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1:3.85, the mixing time of a high-speed mixer is 32min, the melt extrusion temperature is 226 ℃, and the pressure is 5 MPa;

(3) preparing polyester fiber with fluorescence and flame retardant functions:

the mixture of the functional master batch and the PET slices with the intrinsic viscosity of 0.8dl/g is used as a raw material to carry out melt blending spinning to prepare the fluorescent flame-retardant polyester fiber, namely the polyester fiber with both fluorescent and flame-retardant functions; wherein the mass ratio of the functional master batch to the PET slices is 1: 13.3;

the melt blending spinning process comprises the following steps: the spinning temperature is 289 ℃; the temperature of the cross air blow is 28 ℃, and the air speed of the cross air blow is 0.5 m/s; the winding spinning speed is 3628 m/min; the draw ratio was 4.0.

The fineness of the finally prepared polyester fiber with the fluorescent and flame-retardant functions is 4dtex, the breaking strength is 4.2cN/dtex, and the elongation at break is 14.2%; the fluorescence quantum yield is 62%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under the excitation of the wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 31, and the vertical burning grade is UL 94V-0 grade.

Example 14

(1) preparing fluorescent flame-retardant microspheres:

(1.1) mixing dioctyl sodium sulfosuccinate and deionized water at a temperature T1(55 ℃) to form a system I;

(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene imide derivative (prepared in example 6) in xylene, adding the mixture into the system I, and mixing at the temperature of T2(95 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 6 wt%, the content of 1, 7-vinyl-perylene imide derivatives is 9 wt%, the content of xylene is 9.3 wt%, and the content of dioctyl sodium sulfosuccinate is 0.7 wt%;

(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 8h, and the polymerization temperature is 95 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 3; heating and refluxing for 11h, and drying at 110 deg.C;

the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 21: 125; the average diameter of the polyacrylic acid microspheres is 300nm, the average pore diameter is 30nm, and the porosity is 55%; the fluorescence quantum yield of the polyacrylic acid microspheres is 99%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;

(1.5) dispersing polyacrylic acid microspheres in chloroform to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 20%;

(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 12h, and the drying temperature is 40 ℃;

(2) preparing functional master batches:

adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer for mixing and preparing functional master batches through melt extrusion; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional master batch is 1:5.25, the mixing time of a high-speed mixer is 40min, the temperature of melt extrusion is 250 ℃, and the pressure is 6 MPa;

(3) preparing polyester fiber with fluorescence and flame retardant functions:

the mixture of the functional master batch and the PET slices with the intrinsic viscosity of 0.7dl/g is used as a raw material to carry out melt blending spinning to prepare the fluorescent flame-retardant polyester fiber, namely the polyester fiber with both fluorescent and flame-retardant functions; wherein the mass ratio of the functional master batch to the PET slices is 1: 13.3;

the melt blending spinning process comprises the following steps: the spinning temperature is 295 ℃; the temperature of the cross air blow is 30 ℃, and the air speed of the cross air blow is 0.5 m/s; the winding spinning speed is 4000 m/min; the draw ratio was 4.0.

The fineness of the finally prepared polyester fiber with the functions of fluorescence and flame retardance is 4dtex, the breaking strength is 4.5cN/dtex, and the elongation at break is 13.2%; the fluorescence quantum yield is 80%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under the excitation of the wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 35, and the vertical burning grade is UL 94V-0 grade.

Claims

1. A polyester fiber with both fluorescent and flame-retardant functions is characterized in that: mainly comprises a polyester matrix and fluorescent flame-retardant microspheres dispersed in the polyester matrix;

the fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;

the 1, 7-vinyl-perylene bisimide derivative is perylene bisimide of which gulf positions are 1 and 7 substituted groups with ethylene groups and imide positions are substituted groups with large volumes;

the bulky substituent is sesqui-cage siloxane 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

the substituent of the ethylene group is an alkyl chain with an ethylene group at the terminal, and the alkyl chain is less than six carbons.

2. The polyester fiber with both fluorescent and flame-retardant functions as claimed in claim 1, wherein the polyacrylic acid microsphere has a molar ratio of 1, 7-vinyl-perylene imide derivative to acrylic acid structural units of 14-21.5: 125.

3. The polyester fiber with both fluorescence and flame retardant functions according to claim 1, wherein the fluorescent quantum yield of the polyacrylic acid microsphere is 95-99%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with a wavelength of 630-645 nm is generated under excitation with a wavelength of 440-460 nm; the average diameter of the polyacrylic acid microspheres is 150-300 nm, the average pore diameter is 10-30 nm, and the porosity is 35-55%; the phosphorus content in the fluorescent flame-retardant microspheres is 3.75-25 wt%, and the zinc content is 1.25-15 wt%.

4. The fluorescent and flame-retardant polyester fiber according to claim 1, wherein the fluorescent and flame-retardant polyester fiber has a fineness of 3.2 to 4dtex, a breaking strength of 3 to 4.5cN/dtex, and an elongation at break of 13.2 to 17.4%; the fluorescence quantum yield is 60-80%, and a characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the flame retardant property is as follows: the limiting oxygen index LOI value is 30-35, and the vertical burning grade is UL 94V-0 grade.

5. The method for preparing the polyester fiber with the functions of fluorescence and flame retardance as claimed in any one of claims 1 to 4, wherein the method comprises the following steps: adding the fluorescent flame-retardant microspheres and PET resin powder into a high-speed mixer, mixing, performing melt extrusion to obtain functional master batches, and performing melt blending spinning by taking the mixture of the functional master batches and PET slices as a raw material to obtain fluorescent flame-retardant polyester fibers, namely the polyester fibers with the fluorescent and flame-retardant functions;

(3) firstly, adding potassium persulfate into a system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres;

(4) mixing polyacrylate microspheres with a sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres;

(6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dripping deionized water at a certain speed to obtain a mixed solution;

(7) and filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres.

6. The preparation method of the polyester fiber with the fluorescent and flame-retardant functions according to claim 5, wherein the mass ratio of the fluorescent flame-retardant microspheres to the PET resin powder in the functional masterbatch is 1: 1.85-5.25; and during melt blending spinning, the mass ratio of the functional master batch to the PET chips is 1: 11.5-13.3.

7. The preparation method of the polyester fiber with the fluorescent and flame-retardant functions as claimed in claim 5, wherein the melt extrusion temperature is 220-250 ℃, and the pressure is 4-6 MPa; the melt blending spinning process comprises the following steps: the spinning temperature is 270-295 ℃; the temperature of the cross air blow is 28-30 ℃, and the air speed of the cross air blow is 0.3-0.5 m/s; the winding spinning speed is 3500-4000 m/min; the drafting multiplying power is 3.0-4.0;

the intrinsic viscosity of the PET slices is 0.6-0.9 dl/g;

the mixing time of the high-speed mixer is 30-40 min.

8. The method for preparing polyester fiber with fluorescent and flame retardant functions according to claim 5, wherein the emulsifier is potassium laurate, sodium dodecyl sulfate or sodium dioctyl sulfosuccinate; the organic solvent is toluene or xylene.

9. The preparation method of the polyester fiber with the fluorescent and flame-retardant functions as claimed in claim 5, wherein in the step (1), T1 is 35-55 ℃;

in the system II in the step (2), the content of the emulsifier is 0.4-0.7 wt%, the content of the methyl acrylate is 4-6 wt%, the content of the 1, 7-vinyl-perylene imide derivative is 9-15 wt%, and the content of the organic solvent is 6-10 wt%; t2 is 75-95 ℃; in the step (3), the addition amount of the potassium persulfate is 1-5 wt% of the polyacrylate dispersion liquid; the polymerization time is 4-8 h, and the polymerization temperature is 75-95 ℃;