CN111074363B

CN111074363B - Superfine polyester fluorescent fiber with high adsorption function and preparation method thereof

Info

Publication number: CN111074363B
Application number: CN201911392442.4A
Authority: CN
Inventors: 顾益明; 朱美芳; 黄新强; 孙宾; 顾洪达; 金开元; 李俊
Original assignee: Changshu Polyester Co ltd; Donghua University
Current assignee: Changshu Polyester Co ltd; Donghua University
Priority date: 2019-12-30
Filing date: 2019-12-30
Publication date: 2022-04-15
Anticipated expiration: 2039-12-30
Also published as: CN111074363A

Abstract

The invention relates to a high-adsorption function superfine polyester fluorescent fiber and a preparation method thereof, in particular to a high-adsorption function superfine polyester fluorescent fiber based on sulfonic acid functionalized polystyrene microspheres and a preparation method thereof. The specific surface area of the fiber is large, and the sulfonic acid functionalized polystyrene fluorescent microspheres are uniformly dispersed in the polyester matrix, so that the fiber is provided with sulfonic acid groups. The invention overcomes the difficulty of low sodium sulfonate load rate in polyester in the prior art, improves the sodium sulfonate load rate of polyester by mixing the microspheres with high load rate into the polyester, and ensures that the obtained polyester fiber has higher adsorption energy due to the large specific surface area of the superfine fiber.

Description

Superfine polyester fluorescent fiber with high adsorption function and preparation method thereof

Technical Field

The invention belongs to the technical field of fiber preparation, and relates to a superfine polyester fluorescent fiber with high adsorption function based on sulfonic acid functionalized polystyrene microspheres and a preparation method thereof

Background

Heavy metals are indispensable 'micronutrients' for human health, are widely present in human muscles and bones, and play an important role in human life activities and metabolic processes. However, when the content of these heavy metals is high, the toxic effect on human body is generated. In recent years, due to the continuous progress of society and the continuous development of industry, the exceeding of heavy metal content in sewage, sludge and soil causes potential harm to the environment. After the heavy metals invade the human body, the heavy metals do not have the same effect on each organ and have direct toxic effect on partial organs.

At present, methods for efficiently and quickly removing heavy metal ions in water include a chemical precipitation method, a membrane separation technology, an ion exchange method, a reverse osmosis method, an electrodialysis method, a micro-electrolysis method, an electrodeionization technology, an adsorption method and the like. The methods or the technologies have respective advantages, but have respective disadvantages, for example, the membrane separation method has the problems of poor stability, difficult cleaning, high treatment cost and the like, and the anti-fouling performance, the separation performance and the service life of the membrane material still need to be improved; the chemical precipitation method is not suitable for treating wastewater with low concentration of heavy metal ions, is easily limited by environment and medicament, the treated water still needs to be further treated, and the precipitate generated in the reaction process is easy to cause environmental pollution; the electrodialysis method is easy to generate concentration polarization and scale formation in the operation process, so the ion exchange membrane needs to be cleaned or replaced frequently; ion exchange resins are expensive and susceptible to contamination; in contrast, the adsorption method has the advantages of large adsorption capacity, high selectivity, wide raw materials, easy regeneration and the like, and gradually draws attention in the field of heavy metal wastewater treatment.

The activated carbon is a common heavy carbon-based metal adsorbent, and has high adsorption capacity due to large specific surface area and pore volume. And the water treatment agent is widely applied to water treatment due to good chemical stability and good durability. The utilization of heavy metal adsorption depends on surface acidity and special surface functional groups to a great extent, and the heavy metal ions in the water body are separated through ion exchange, electrostatic interaction, complexation, redox reaction and the like with the heavy metal ions. However, due to the shortage of coal resources, the price of commercial activated carbon in China is continuously increased, and the cost for treating heavy metal wastewater by using the commercial activated carbon is also continuously increased, so that the application of the activated carbon in water treatment is limited to a great extent.

The chelate fiber is a fibrous adsorbent following chelate resin, and has different coordination atoms and functional groups due to the variety of available matrixes and modification methods, so that the selective adsorption of heavy metal ions is realized. However, the preparation method of the chelate fiber is complex, and the property control of the fiber is difficult. The chitosan is a natural chelating polymer containing amino, can be doped in fibers to prepare a chelating electrospun fiber membrane. The chelate fiber is easy to prepare and can be made into felt or fabric, which greatly improves the contact efficiency with the medium. But the mechanical properties of chitosan fibers are not very good. The fiber with adsorption property needs to introduce functional groups with adsorption property into the fiber, and needs to increase the contact area (surface area) of the fiber and a mobile phase. ,

therefore, the research on the superfine polyester fluorescent fiber with low cost, easy preparation, high adsorption function and excellent mechanical property and the preparation method thereof have very important significance.

Disclosure of Invention

The invention aims to solve the technical problems of high production cost, difficult preparation, low adsorption function, poor mechanical property and the like in superfine polyester fiber with adsorption function in the prior art, and provides superfine polyester fluorescent fiber with high adsorption function based on sulfonic acid functionalized polystyrene microspheres and a preparation method thereof

The invention aims to provide the superfine polyester fluorescent fiber which is low in production cost, easy to prepare, high in adsorption capacity and excellent in mechanical property, and the superfine polyester fluorescent fiber is prepared by adding a 1, 7-vinyl-perylene bisimide derivative into styrene for emulsion polymerization, then carrying out sulfonic acid functionalization treatment to obtain sulfonic acid functionalized polystyrene high-fluorescence microspheres, and then melting the sulfonic acid functionalized polystyrene high-fluorescence microspheres and polyester chips on a screw to obtain a spinning melt of polyester fibers. And (3) feeding polyamide-6 or polyamide-66 into the screw separately for melting to obtain the spinning melt of the nylon fiber. And then, metering the two obtained spinning melts, and sending the two spinning melts into a composite spinning box to obtain the polyester-nylon composite oriented yarn. And finally false twisting and deforming the polyester-nylon composite oriented yarn to obtain the fluorescent polyester-nylon composite superfine fiber product.

The invention also aims to provide a preparation method of the superfine polyester fluorescent fiber with high adsorption function based on the sulfonic acid functionalized polystyrene microsphere.

The fiber of the invention is a superfine polyester fluorescent fiber with high adsorption function. The fiber has excellent adsorption function.

The fibers comprise sulfonic acid functionalized polystyrene high fluorescence microspheres. The mass percentage of the fluorescent microspheres in the polyester fiber is 7-10%, and the filament number obtained after fiber splitting is 0.20-0.50 dtex; the maximum adsorption capacity reaches 140-170 mg/g.

The load refers to that sulfonic acid functional groups are introduced into the polyester fibers through polystyrene high-fluorescence microspheres functionalized by doping sulfonic acid;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere taking 1, 7-vinyl-perylene bisimide derivatives as a cross-linking agent; the polystyrene has a sodium sulfonate functional group;

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

As a preferred technical scheme:

the high adsorption function superfine polyester fluorescent fiber is characterized in that the bulky substituent is sesquialter cage-shaped siloxane and/or long alkyl chain with side chain;

the silsesquioxane is

R is isobutyl or isooctyl;

the long alkyl with side chainThe basic chain is

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. The chain length of the alkyl chain connecting the vinyl and the perylene imide structure cannot be overlong, the ethylene group has a wide movement range in a reaction system after overlong, the possibility of encountering an adjacent ethylene group is higher, and the self-polymerization caused by mutual collision of the ethylene groups in the 1, 7-vinyl-perylene imide derivative is avoided, so that the length of the alkyl chain cannot be overlong.

According to the cationic dyeable polyester fiber, the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit is 1: 4-1: 3, and the addition amount of the 1, 7-vinyl-perylene imide derivative is too small, so that microspheres are difficult to form; the loading capacity of the sodium sulfonate functional group is 2.0-3.0 mmol/g, the sodium sulfonate loading capacity is directly related to the adsorption function, but the maximum loading capacity can only reach 3.0mmol/g under the influence of the sulfonation efficiency.

In the superfine polyester fluorescent fiber with high adsorption function, the average diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 100-300nm, and the pore size variance is 0.8-1.6; the specific surface area is 800-²g^-1(ii) a The yield of the fluorescence quantum is 60-80%.

The superfine polyester fluorescent fiber with high adsorption function has the elongation at break of 20-38 percent and the composite fiber fineness of 150-180 dtex.

The invention also provides a preparation method of the superfine polyester fluorescent fiber with high adsorption function, which comprises the steps of melting and extruding components which are mixed for 25-35min at the temperature of 220-225 ℃ by 35-45 wt% of PET powder, 40-60 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 5-10 wt% of calcium stearate and 1-5 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol to prepare functional master batches of the fluorescent microspheres with the sulfonic acid functional group;

and (3) feeding polyamide-6 or polyamide-66 into the screw separately for melting to obtain the spinning melt of the nylon fiber. Then, measuring 15-30% of the nylon fiber spinning melt, 70-85% of the master batch added with the fluorescent microspheres and the pure polyester fiber melt according to the weight percentage of the two obtained spinning melts, so that the fluorescent microspheres account for 7-10% of the mass of the polyester fiber, then sending the polyester fiber spinning melt into a composite spinning box, spinning the polyester fiber spinning melt through a distribution plate, a spinneret plate and the like of a spinning assembly in the box in sequence, and then cooling, oiling and winding the polyester fiber spinning melt to obtain the polyester fiber and nylon composite oriented yarn; wherein the temperature of the melt conveying pipeline is 255-275 ℃, the temperature of the spinning manifold is 260-275 ℃, the lateral blowing air speed is 0.3-0.8m/s, the temperature of the hot roller is 130-17 ℃, and the spinning speed is 2500-3500 m/min. Eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the polyamide fibers are formed on the distribution plate to form a shape like a Chinese character 'mi', the aperture of each distribution hole is 0.24-0.30mm, and the groove width, the groove depth and the groove length of each distribution groove are 0.3-0.35mm, 0.28-0.32mm and 5-6mm in sequence; and finally false twisting and deforming the polyester-nylon composite oriented yarn to obtain the fluorescent composite superfine fiber product. And (3) obtaining the fluorescent superfine fiber on a liquid flow coloring agent through alkali decrement and mechanical fiber opening.

The preparation method of the superfine polyester fluorescent fiber with high adsorption function comprises the following steps of:

(1) mixing styrene, 1, 7-vinyl-perylene imide derivatives, peroxide initiator and organic pore-making agent to obtain a mixture;

(2) adding the mixture into deionized water and 0.5-3.0 wt% of emulsion under stirring, rapidly heating to T, and stopping reaction after a period of time to obtain emulsion;

(3) adding 1.5-10 wt% of sodium chloride demulsifier into the emulsion under the condition of stirring, coagulating, filtering, washing with hot water, and drying at the temperature higher than the boiling point of the pore-forming agent to obtain the sulfonic acid functionalized polystyrene high-fluorescence microsphere.

In the preparation method of the superfine polyester fluorescent fiber with high adsorption function, the peroxide initiator is dibenzoyl oxide (BPO) or diethylhexyl dicarbonate oxide (EHP); the organic pore-making agent is toluene, and the mass ratio of the peroxide initiator to the styrene is 1: 75-85; the molar ratio of the 1, 7-vinyl-perylene bisimide derivative of the styrene is 3-4: 1; the mass ratio of the organic pore-forming agent to the styrene is 1: 1-4;

the mass ratio of the mixture to the deionized water is 1: 5-7, T is 75-90 ℃, and the time is 2-6 hours.

The preparation method of the superfine polyester fluorescent fiber with the high adsorption function comprises the following steps of:

(a) placing the polystyrene high-fluorescence microspheres in an organic solvent for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting for 5-10 h at the temperature of 95-100 ℃, and removing the solvent and the residual sulfuric acid to obtain sulfonated polystyrene high-fluorescence microspheres;

(b) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution, and reacting at the temperature of 20-30 ℃ for 0.5-2 h to obtain sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the organic solvent is dichloroethane, toluene, xylene or tetrahydrofuran;

the mass ratio of the polystyrene high-fluorescence microspheres to the organic solvent is 1: 1-1.5;

the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 3-6;

the concentration of the sodium hydroxide solution is 0.1-5 wt%;

the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1: 2-5;

washing with water 10 times larger than the volume of the microspheres to remove concentrated sulfuric acid, and drying at a temperature higher than the boiling point of the organic solvent to remove residual organic solvent.

The invention uses sulfonic acid functionalized fluorescent microspheres as an added filler, adopts a composite superfine fiber preparation method, and obtains the superfine fiber with large specific surface area after fiber opening treatment (the fiber opening method refers to CN 105506879). The porous sulfonic acid functionalized polystyrene microspheres added in the superfine fiber have the strong adsorption capacity for metal ions due to the existence of the sulfonic acid functional groups and the further improvement of the specific surface area of the fiber by the porous structure, so more sulfonic acid groups exposed in the air in unit volume of the material. The functional microspheres are added, so that the fluorescent fiber is more convenient than a chemically modified fluorescent fiber, can be used for various fiber matrixes, and can be endowed with multiple functions. As the sulfonic acid modified microspheres are polystyrene microspheres, the benzene ring structure in the microspheres and the benzene ring structure in the polyester system have strong interaction, so that the good dispersion of the microspheres in the polyester matrix has little influence on the spinning forming. The sodium sulfonate group is mainly connected into a benzene ring structure, the benzene ring structure of polystyrene is rich, and the density of the benzene ring in polyester is not high as that of polystyrene, so that the loading capacity of the polystyrene microsphere on the sodium sulfonate functional group is far greater than that of the polyester. When the sodium sulfonate functionalized microspheres are used as an additive, the master batch with high addition amount is prepared, and then the polyester fiber with high load rate is obtained by melt blending spinning molding, and the sulfonic acid load capacity of the fiber is large. Because polystyrene and polyester both contain benzene ring structures, the polystyrene microsphere has good compatibility in the polyester, and the porous structure of the microsphere further increases the interaction area of the microsphere and the polyester, so that the polystyrene microsphere has good bonding property with the fiber and has small influence on the mechanical property of the finally formed fiber.

Has the advantages that:

the superfine polyester fluorescent fiber with high adsorption function has large specific surface area, a sulfonic acid group in the structure and strong adsorption capacity.

The preparation method is simple and economical.

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.

Fluorescence quantum yield method: fluorescence Quantum yield (Quantum Yields) is an important luminescence parameter of a fluorescent substance, defined as the ratio of the number of photons emitted after absorption of light by the fluorescent substance to the number of photons of the absorbed excitation light. In the experiment, a fluoroSENS steady-state fluorescence spectrometer is selected to measure the quantum yield of the fluorescent microspheres. The instrument adopts the latest single photon counting technology, greatly improves the sensitivity of the system, effectively inhibits stray light through the design of a light path, an instrument structure, an optical filter and the like, has the stray light inhibition ratio as high as 10 < -5 >, and fundamentally eliminates the interference and influence on a fluorescence spectrum. Different from the traditional contrast test method, the fluoroSENS adopts an integrating sphere to measure the absolute quantum yield of a sample, and adopts a three-step measurement method:

(1) exciting light scanning, namely, setting parameters and operating the parameters when no sample exists in the integrating sphere, and scanning the exciting light after the parameters are operated in place;

(2) emission spectrum scanning-after excitation spectrum scanning is finished, a sample is placed in the integrating sphere and placed on the position of excitation light for emission spectrum scanning;

(3) secondary emission spectrum scanning, namely after the emission spectrum scanning is finished, placing a sample in an integrating sphere, pulling out a sample holder pull rod, and performing secondary emission spectrum scanning when the sample is not in an excitation light beam; compared with the traditional quantum yield testing method, the method adopts the integrating sphere to measure the absolute quantum yield of the sample, so that the accuracy of the measuring result is further improved.

Example 1

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

(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). 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

(0.50mmol) 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 (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 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-215.00mL of pyrrolidone (NMP) and stirring at 25 ℃ for 1h after dissolving the solid. Is then added

Example 3

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

the crude product was charged to a 250mL three-necked flaskPTCDA-Br

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,

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

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. Is then added

Example 7

A preparation method of superfine polyester fluorescent fiber with high adsorption function comprises the following steps:

(1) preparing the polystyrene high-fluorescence microspheres:

(1.1) mixing styrene, 1, 7-vinyl-perylene imide derivative (obtained from example 1), dibenzoyl oxide (BPO) and toluene to obtain a mixture; wherein the mass ratio of dibenzoyl oxide (BPO) to styrene is 1: 75; the molar ratio of styrene to 1, 7-vinyl-perylene imide derivative is 3: 1; the mass ratio of toluene to styrene is 1: 1;

(1.2) adding deionized water (the mass ratio of the mixture to the deionized water is 1:5) and 00.5 wt% of emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, rapidly heating to 75 ℃, keeping for 5 hours, and stopping the reaction to obtain emulsion;

and (1.3) adding 1.5 wt% of sodium chloride serving as a demulsifier into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying at the temperature higher than the boiling point of toluene to obtain the polystyrene high-fluorescence microspheres.

(2) Placing the polystyrene high-fluorescence microspheres in dichloroethane for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting for 10 hours at the temperature of 95 ℃, and removing the solvent and the residual sulfuric acid to obtain the sulfonated polystyrene high-fluorescence microspheres; wherein the mass ratio of the polystyrene high-fluorescence microspheres to dichloroethane is 1: 1; the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 3;

(3) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution with the concentration of 0.1 wt% (the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1:2), reacting for 2 hours at the temperature of 20 ℃, washing with water with the volume being 10 times that of the microspheres to remove concentrated sulfuric acid, and drying at the temperature higher than the boiling point of dichloroethane to remove residual dichloroethane to obtain sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes 1, 7-vinyl-perylene imide derivative as a cross-linking agent and has sulfonic acid functional groups; the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 100nm, and the aperture variance is 0.8; specific surface area of 950m²g^-1(ii) a The fluorescence quantum yield is 65%; the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit in the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 1: 3; the loading capacity of the sodium sulfonate functional group is 2 mmol/g;

(4) mixing 35 wt% of PET powder, 40 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 5 wt% of calcium stearate and 1 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol; melting and extruding the components after mixing for 25min at 220 ℃ to prepare functional master batches of the fluorescent microspheres containing sulfonic acid functional groups;

and (3) feeding polyamide-6 into the screw separately for melting to obtain a spinning melt of the polyamide fiber.

Measuring 15% of nylon fiber spinning melt, 70% of master batch added with fluorescent microspheres and pure polyester fiber melt according to the weight percentage (so that the mass percentage of the fluorescent microspheres in the polyester fiber is 7%); then the mixture is sent into a composite spinning box, and is sequentially spun through a distribution plate, a spinneret plate and the like of a spinning assembly in the box, and then is cooled, oiled and wound to form composite oriented yarn through measuring and blowing; the distribution plate is provided with eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the polyamide fibers to form a shape like a Chinese character 'mi', the aperture of each distribution hole is 24mm, and the width, depth and length of each distribution groove are 0.3mm, 0.28mm and 5mm in sequence. The temperature of the melt conveying pipeline is 255 ℃, the temperature of the spinning manifold is 260 ℃, the air speed of the cross air blow is 0.3m/s, the temperature of the hot roll is 130 ℃, and the spinning speed is 3280 m/min.

False twist texturing is carried out on the obtained composite oriented yarn, and the fluorescent composite fiber product is obtained.

And (3) performing alkali decrement and mechanical fiber opening on the product fluorescent composite fiber on a liquid flow coloring agent to obtain the superfine polyester fluorescent fiber with the high adsorption function.

The prepared superfine polyester fluorescent fiber with high adsorption function contains sulfonic acid functionalized polystyrene high-fluorescence microspheres; obtaining the filament number of 0.2dtex after opening; the maximum adsorption capacity reaches 140 mg/g; the high-adsorption-function superfine polyester fluorescent fiber has the breaking elongation of 24 percent and the fineness of the composite fiber of 150 dtex.

Example 8

(1) preparing the polystyrene high-fluorescence microspheres:

(1.1) mixing styrene, 1, 7-vinyl-perylene imide derivative (obtained from example 2), dibenzoyl oxide (BPO) and toluene to obtain a mixture; wherein the mass ratio of dibenzoyl oxide (BPO) to styrene is 1: 75; the molar ratio of styrene to 1, 7-vinyl-perylene imide derivative is 3: 1; the mass ratio of toluene to styrene is 1: 1;

(1.2) adding deionized water (the mass ratio of the mixture to the deionized water is 1:7) and 02.9 wt% of an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, rapidly heating to 82 ℃, and stopping the reaction after 3 hours to obtain an emulsion;

and (1.3) adding 9.5 wt% of sodium chloride serving as a demulsifier into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying at the temperature higher than the boiling point of toluene to obtain the polystyrene high-fluorescence microspheres.

(2) Placing the polystyrene high-fluorescence microspheres in dichloroethane for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting for 9 hours at the temperature of 95 ℃, and removing the solvent and the residual sulfuric acid to obtain the sulfonated polystyrene high-fluorescence microspheres; wherein the mass ratio of the polystyrene high-fluorescence microspheres to dichloroethane is 1: 1.1; the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 3;

(3) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution with the concentration of 2.7 wt% (the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1:3), reacting for 1.2h at the temperature of 22 ℃, washing with water with the volume being 10 times that of the microspheres to remove concentrated sulfuric acid, and drying at the temperature higher than the boiling point of dichloroethane to remove residual dichloroethane to obtain sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes 1, 7-vinyl-perylene imide derivative as a cross-linking agent and has sulfonic acid functional groups; the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 249nm, and the aperture variance is 1.4; specific surface area of 900m²g^-1(ii) a The fluorescence quantum yield is 72%; the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit in the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 1: 3; the loading capacity of the sodium sulfonate functional group is 2 mmol/g;

(4) mixing 44 wt% of PET powder, 57 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 7 wt% of calcium stearate and 4 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol; melting and extruding the components after mixing for 27min at 224 ℃ to prepare functional master batches of the fluorescent microspheres containing sulfonic acid functional groups;

and (3) feeding the polyamide-66 into the screw separately for melting to obtain a spinning melt of the polyamide fiber.

Metering 16% of nylon fiber spinning melt, 84% of master batch added with fluorescent microspheres and pure polyester fiber melt according to the weight percentage (so that the mass percentage of the fluorescent microspheres in the polyester fiber is 7%); then the mixture is sent into a composite spinning box, and is sequentially spun through a distribution plate, a spinneret plate and the like of a spinning assembly in the box, and then is cooled, oiled and wound to form composite oriented yarn through measuring and blowing; eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the nylon fibers are formed in the distribution plates to form a shape like a Chinese character 'mi', the aperture of each distribution hole is 28mm, and the width, depth and length of each distribution groove are 0.33mm, 0.29mm and 5mm in sequence. The temperature of the melt conveying pipeline is 266 ℃, the temperature of the spinning manifold is 271 ℃, the air speed of the cross air blow is 0.4m/s, the temperature of the hot roll is 152 ℃, and the spinning speed is 2690 m/min.

The prepared superfine polyester fluorescent fiber with high adsorption function contains sulfonic acid functionalized polystyrene high-fluorescence microspheres; obtaining the filament number of 0.2dtex after opening; the maximum adsorption capacity reaches 140 mg/g; the high-adsorption superfine polyester fluorescent fiber has the breaking elongation of 36 percent and the fineness of a composite fiber of 161 dtex.

Example 9

(1) preparing the polystyrene high-fluorescence microspheres:

(1.1) mixing styrene, 1, 7-vinyl-perylene imide derivative (obtained from example 1), dibenzoyl oxide (BPO) and toluene to obtain a mixture; wherein the mass ratio of dibenzoyl oxide (BPO) to styrene is 1: 81; the molar ratio of styrene to 1, 7-vinyl-perylene imide derivative is 4: 1; the mass ratio of toluene to styrene is 1: 4;

(1.2) adding deionized water (the mass ratio of the mixture to the deionized water is 1:5) and 02.9 wt% of an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, rapidly heating to 83 ℃, and stopping the reaction after 3 hours to obtain an emulsion;

and (1.3) adding 6.9 wt% of sodium chloride demulsifier into the emulsion under the stirring condition, filtering after stirring and coagulating, washing with hot water, and drying at the temperature of more than the boiling point of toluene to obtain the polystyrene high-fluorescence microsphere.

(2) Placing the polystyrene high-fluorescence microspheres in tetrahydrofuran for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting at the temperature of 95 ℃ for 9 hours, and removing the solvent and the residual sulfuric acid to obtain sulfonated polystyrene high-fluorescence microspheres; wherein the mass ratio of the polystyrene high-fluorescence microspheres to tetrahydrofuran is 1: 1.5; the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 3;

(3) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution with the concentration of 4.8 wt% (the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1:5), reacting for 0.6h at the temperature of 29 ℃, washing with water with the volume being 10 times that of the microspheres to remove concentrated sulfuric acid, and drying at the temperature higher than the boiling point of tetrahydrofuran to remove residual tetrahydrofuran to obtain sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes 1, 7-vinyl-perylene imide derivative as a cross-linking agent and has sulfonic acid functional groups; the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 253nm, and the aperture variance is 1.2; specific surface area of 880m²g^-1(ii) a The fluorescence quantum yield is 73%; the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit in the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 1: 4; the loading capacity of the sodium sulfonate functional group is 2 mmol/g;

(4) mixing 44 wt% of PET powder, 52 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 6 wt% of calcium stearate and 4 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol; melting and extruding the components after being mixed for 34min at 221 ℃ to prepare functional master batches of the fluorescent microspheres containing sulfonic acid functional groups;

Measuring 19% of nylon fiber spinning melt, 81% of master batch added with fluorescent microspheres and pure polyester fiber melt according to the weight percentage (so that the mass percentage of the fluorescent microspheres in the polyester fiber is 7%); then the mixture is sent into a composite spinning box, and is sequentially spun through a distribution plate, a spinneret plate and the like of a spinning assembly in the box, and then is cooled, oiled and wound to form composite oriented yarn through measuring and blowing; eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the nylon fibers are formed in the distribution plates to form a rice-shaped distribution groove, the aperture of each distribution hole is 27mm, and the groove width, the groove depth and the groove length of each distribution groove are 0.3mm, 0.32mm and 6mm in sequence. The temperature of the melt conveying pipeline is 262 ℃, the temperature of the spinning manifold is 264 ℃, the air speed of the cross air blow is 0.4m/s, the temperature of the hot roll is 164 ℃, and the spinning speed is 2640 m/min.

The prepared superfine polyester fluorescent fiber with high adsorption function contains sulfonic acid functionalized polystyrene high-fluorescence microspheres; obtaining the filament number of 0.2dtex after opening; the maximum adsorption capacity reaches 140 mg/g; the high-adsorption-function superfine polyester fluorescent fiber has the elongation at break of 38 percent and the fineness of the composite fiber of 169 dtex.

Example 10

(1) preparing the polystyrene high-fluorescence microspheres:

(1.1) mixing styrene, 1, 7-vinyl-perylene imide derivative (obtained from example 3), dibenzoyl oxide (BPO) and toluene to obtain a mixture; wherein the mass ratio of dibenzoyl oxide (BPO) to styrene is 1: 82; the molar ratio of styrene to 1, 7-vinyl-perylene imide derivative is 4: 1; the mass ratio of toluene to styrene is 1: 4;

(1.2) adding deionized water (the mass ratio of the mixture to the deionized water is 1:5) and 00.6 wt% of an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, rapidly heating to 75 ℃, keeping the temperature for 6 hours, and stopping the reaction to obtain an emulsion;

and (1.3) adding 5.4 wt% of sodium chloride serving as a demulsifier into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying at the temperature higher than the boiling point of toluene to obtain the polystyrene high-fluorescence microspheres.

(2) Placing the polystyrene high-fluorescence microspheres in tetrahydrofuran for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting for 9 hours at the temperature of 96 ℃, and removing the solvent and the residual sulfuric acid to obtain sulfonated polystyrene high-fluorescence microspheres; wherein the mass ratio of the polystyrene high-fluorescence microspheres to tetrahydrofuran is 1: 1.2; the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 4;

(3) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution with the concentration of 2.1 wt% (the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1:3), reacting for 1.8h at the temperature of 22 ℃, washing with water with the volume being 10 times that of the microspheres to remove concentrated sulfuric acid, and drying at the temperature higher than the boiling point of tetrahydrofuran to remove residual tetrahydrofuran to obtain sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes 1, 7-vinyl-perylene imide derivative as a cross-linking agent and has sulfonic acid functional groups; the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 150nm, and the aperture variance is 1.2; the specific surface area is 930m²g^-1(ii) a The fluorescence quantum yield is 65%; the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit in the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 1: 4; the loading capacity of the sodium sulfonate functional group is 2.2 mmol/g;

(4) mixing 43 wt% of PET powder, 58 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 6 wt% of calcium stearate and 1 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol; melting and extruding the components after mixing for 25min at 224 ℃ to prepare functional master batches of the fluorescent microspheres containing sulfonic acid functional groups;

Measuring 19% of nylon fiber spinning melt, 81% of master batch added with fluorescent microspheres and pure polyester fiber melt according to the weight percentage (so that the mass percentage of the fluorescent microspheres in the polyester fiber is 7%); then the mixture is sent into a composite spinning box, and is sequentially spun through a distribution plate, a spinneret plate and the like of a spinning assembly in the box, and then is cooled, oiled and wound to form composite oriented yarn through measuring and blowing; eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the nylon fibers are formed in the distribution plates to form a shape like a Chinese character 'mi', the aperture of each distribution hole is 27mm, and the width, depth and length of each distribution groove are 0.3mm, 0.31mm and 5mm in sequence. The temperature of the melt conveying pipeline is 265 ℃, the temperature of the spinning manifold is 270 ℃, the air speed of the cross air blow is 0.5m/s, the temperature of the hot roll is 148 ℃, and the spinning speed is 2800 m/min.

The prepared superfine polyester fluorescent fiber with high adsorption function contains sulfonic acid functionalized polystyrene high-fluorescence microspheres; obtaining the filament number of 0.2dtex after opening; the maximum adsorption capacity reaches 159 mg/g; the high-adsorption superfine polyester fluorescent fiber has the elongation at break of 33 percent and the fineness of the composite fiber of 178 dtex.

Example 11

(1) preparing the polystyrene high-fluorescence microspheres:

(1.1) mixing styrene, 1, 7-vinyl-perylene imide derivative (obtained from example 4), diethylhexyl dicarbonate oxide (EHP) and toluene to obtain a mixture; wherein the mass ratio of diethylhexyl dicarbonate oxide (EHP) to styrene is 1: 77; the molar ratio of styrene to 1, 7-vinyl-perylene imide derivative is 4: 1; the mass ratio of toluene to styrene is 1: 4;

(1.2) adding deionized water (the mass ratio of the mixture to the deionized water is 1:6) and 01.4 wt% of an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, rapidly heating to 77 ℃, and stopping the reaction after continuing for 4 hours to obtain an emulsion;

and (1.3) adding 5.2 wt% of sodium chloride serving as a demulsifier into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying at the temperature higher than the boiling point of toluene to obtain the polystyrene high-fluorescence microspheres.

(2) Placing the polystyrene high-fluorescence microspheres in toluene for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting for 7 hours at the temperature of 99 ℃, and removing the solvent and the residual sulfuric acid to obtain sulfonated polystyrene high-fluorescence microspheres; wherein the mass ratio of the polystyrene high-fluorescence microspheres to the toluene is 1: 1.3; the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 4;

(3) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution with the concentration of 3.3 wt% (the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1:3), reacting for 1h at the temperature of 26 ℃, washing with water which is 10 times of the volume of the microspheres to remove concentrated sulfuric acid, and drying at the temperature higher than the boiling point of toluene to remove residual toluene, thereby obtaining sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes 1, 7-vinyl-perylene imide derivative as a cross-linking agent and has sulfonic acid functional groups; the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 249nm, and the aperture variance is 1.6; specific surface area of 880m²g^-1(ii) a The fluorescence quantum yield is 67%; the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit in the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 1: 4; the loading capacity of the sodium sulfonate functional group is 2.2 mmol/g;

(4) mixing 40 wt% of PET powder, 50 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 8 wt% of calcium stearate and 2 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol; melting and extruding the components after mixing for 27min at 225 ℃ to prepare functional master batches of the fluorescent microspheres containing sulfonic acid functional groups;

Metering 18% of nylon fiber spinning melt, 82% of master batch added with fluorescent microspheres and pure polyester fiber melt according to the weight percentage (so that the mass percentage of the fluorescent microspheres in the polyester fiber is 9%); then the mixture is sent into a composite spinning box, and is sequentially spun through a distribution plate, a spinneret plate and the like of a spinning assembly in the box, and then is cooled, oiled and wound to form composite oriented yarn through measuring and blowing; the distribution plate is provided with eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the polyamide fibers to form a shape like a Chinese character 'mi', the aperture of each distribution hole is 27mm, and the width, depth and length of each distribution groove are 0.31mm, 0.31mm and 6mm in sequence. The temperature of the melt conveying pipeline is 269 ℃, the temperature of the spinning manifold is 275 ℃, the air speed of the cross-blown air is 0.5m/s, the temperature of the hot roller is 143 ℃, and the spinning speed is 2500 m/min.

The prepared superfine polyester fluorescent fiber with high adsorption function contains sulfonic acid functionalized polystyrene high-fluorescence microspheres; obtaining the filament number of 0.3dtex after opening; the maximum adsorption capacity reaches 160 mg/g; the high-adsorption-function superfine polyester fluorescent fiber has the elongation at break of 38 percent and the fineness of the composite fiber of 172 dtex.

Example 12

(1) preparing the polystyrene high-fluorescence microspheres:

(1.1) mixing styrene, 1, 7-vinyl-perylene imide derivative (obtained from example 3), diethylhexyl dicarbonate oxide (EHP) and toluene to obtain a mixture; wherein the mass ratio of diethylhexyl dicarbonate oxide (EHP) to styrene is 1: 79; the molar ratio of styrene to 1, 7-vinyl-perylene imide derivative is 4: 1; the mass ratio of toluene to styrene is 1: 3;

(1.2) adding deionized water (the mass ratio of the mixture to the deionized water is 1:6) and 00.8 wt% of an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, rapidly heating to 82 ℃, and stopping the reaction after continuing for 4 hours to obtain an emulsion;

and (1.3) adding 2.2 wt% of sodium chloride serving as a demulsifier into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying at the temperature higher than the boiling point of toluene to obtain the polystyrene high-fluorescence microspheres.

(2) Placing the polystyrene high-fluorescence microspheres in toluene for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting for 6 hours at the temperature of 100 ℃, and removing the solvent and the residual sulfuric acid to obtain sulfonated polystyrene high-fluorescence microspheres; wherein the mass ratio of the polystyrene high-fluorescence microspheres to the toluene is 1: 1.1; the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 4;

(3) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution with the concentration of 4.7 wt% (the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1:4), reacting for 0.7h at the temperature of 27 ℃, washing with water with the volume being 10 times that of the microspheres to remove concentrated sulfuric acid, and drying at the temperature higher than the boiling point of toluene to remove residual toluene, thereby obtaining sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes 1, 7-vinyl-perylene imide derivative as a cross-linking agent and has sulfonic acid functional groups; the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 292nm, and the aperture variance is 1.1; the specific surface area is 800m²g^-1(ii) a The fluorescence quantum yield is 72%; the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit in the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 1: 4; the loading capacity of the sodium sulfonate functional group is 2.7 mmol/g;

(4) mixing 44 wt% of PET powder, 54 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 6 wt% of calcium stearate and 5 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol; melting and extruding the components mixed for 31min at 221 ℃ to prepare functional master batches of the fluorescent microspheres containing sulfonic acid functional groups;

Measuring 29% of nylon fiber spinning melt, 71% of master batch added with fluorescent microspheres and pure polyester fiber melt according to the weight percentage (so that the mass percentage of the fluorescent microspheres in the polyester fiber is 9%); then the mixture is sent into a composite spinning box, and is sequentially spun through a distribution plate, a spinneret plate and the like of a spinning assembly in the box, and then is cooled, oiled and wound to form composite oriented yarn through measuring and blowing; the distribution plate is provided with eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the polyamide fibers to form a shape like a Chinese character 'mi', the aperture of each distribution hole is 30mm, and the width, depth and length of each distribution groove are 0.3mm, 0.29mm and 6mm in sequence. The temperature of the melt conveying pipeline is 263 ℃, the temperature of the spinning manifold is 265 ℃, the air speed of the side blowing is 0.4m/s, the temperature of the hot roll is 159 ℃, and the spinning speed is 2880 m/min.

The prepared superfine polyester fluorescent fiber with high adsorption function contains sulfonic acid functionalized polystyrene high-fluorescence microspheres; obtaining the filament number of 0.3dtex after opening; the maximum adsorption capacity reaches 160 mg/g; the high-adsorption superfine polyester fluorescent fiber has the elongation at break of 28 percent and the titer of composite fiber of 179 dtex.

Example 13

(1) preparing the polystyrene high-fluorescence microspheres:

(1.1) mixing styrene, 1, 7-vinyl-perylene imide derivative (obtained from example 5), diethylhexyl dicarbonate oxide (EHP) and toluene to obtain a mixture; wherein the mass ratio of diethylhexyl dicarbonate oxide (EHP) to styrene is 1: 85; the molar ratio of styrene to 1, 7-vinyl-perylene imide derivative is 4: 1; the mass ratio of toluene to styrene is 1: 1;

(1.2) adding deionized water (the mass ratio of the mixture to the deionized water is 1:7) and 01.7 wt% of an emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, rapidly heating to 88 ℃, and stopping the reaction after 2 hours to obtain an emulsion;

and (1.3) adding 3.1 wt% of sodium chloride serving as a demulsifier into the emulsion under the stirring condition, performing suction filtration after stirring and coagulation, washing with hot water, and drying at the temperature higher than the boiling point of toluene to obtain the polystyrene high-fluorescence microspheres.

(2) Placing the polystyrene high-fluorescence microspheres in dimethylbenzene for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting for 7 hours at the temperature of 96 ℃, and removing the solvent and the residual sulfuric acid to obtain sulfonated polystyrene high-fluorescence microspheres; wherein the mass ratio of the polystyrene high-fluorescence microspheres to the xylene is 1: 1.5; the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 5;

(3) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution with the concentration of 1.6 wt% (the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1:2), reacting for 1.9h at the temperature of 21 ℃, washing with water with the volume being 10 times that of the microspheres to remove concentrated sulfuric acid, and drying at the temperature higher than the boiling point of xylene to remove residual xylene to obtain sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes 1, 7-vinyl-perylene imide derivative as a cross-linking agent and has sulfonic acid functional groups; the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 116nm, and the aperture variance is 1.3; the specific surface area is 940m²g^-1(ii) a The fluorescence quantum yield is 78%; the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit in the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 1: 4; the loading capacity of the sodium sulfonate functional group is 2.8 mmol/g;

(4) mixing 35 wt% of PET powder, 52 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 10 wt% of calcium stearate and 3 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol; melting and extruding the components after mixing for 32min at 221 ℃ to prepare functional master batches of the fluorescent microspheres containing sulfonic acid functional groups;

Metering 21% of nylon fiber spinning melt, 79% of master batch added with fluorescent microspheres and pure polyester fiber melt according to the weight percentage (so that the mass percentage of the fluorescent microspheres in the polyester fiber is 10%); then the mixture is sent into a composite spinning box, and is sequentially spun through a distribution plate, a spinneret plate and the like of a spinning assembly in the box, and then is cooled, oiled and wound to form composite oriented yarn through measuring and blowing; eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the polyamide fibers are formed in the distribution plates to form a rice-shaped distribution groove, the aperture of each distribution hole is 26mm, and the groove width, the groove depth and the groove length of each distribution groove are 0.32mm, 0.31mm and 5mm in sequence. The temperature of the melt conveying pipeline is 257 ℃, the temperature of the spinning manifold is 261 ℃, the air speed of the side blowing is 0.8m/s, the temperature of the hot roller is 132 ℃, and the spinning speed is 2670 m/min.

The prepared superfine polyester fluorescent fiber with high adsorption function contains sulfonic acid functionalized polystyrene high-fluorescence microspheres; obtaining the filament number of 0.5dtex after opening; the maximum adsorption capacity reaches 162 mg/g; the high-adsorption-function superfine polyester fluorescent fiber has the elongation at break of 37 percent and the titer of composite fiber of 165 dtex.

Example 14

(1) preparing the polystyrene high-fluorescence microspheres:

(1.1) mixing styrene, 1, 7-vinyl-perylene imide derivative (obtained from example 6), diethylhexyl dicarbonate oxide (EHP) and toluene to obtain a mixture; wherein the mass ratio of diethylhexyl dicarbonate oxide (EHP) to styrene is 1: 85; the molar ratio of styrene to 1, 7-vinyl-perylene imide derivative is 4: 1; the mass ratio of toluene to styrene is 1: 4;

(1.2) adding deionized water (the mass ratio of the mixture to the deionized water is 1:7) and 03 wt% of emulsion (sodium dodecyl sulfate) into the mixture under the stirring condition, rapidly heating to 90 ℃, keeping for 2 hours, and stopping the reaction to obtain emulsion;

and (1.3) adding 10 wt% of sodium chloride demulsifier into the emulsion under the stirring condition, filtering after stirring and coagulation, washing with hot water, and drying at the temperature higher than the boiling point of toluene to obtain the polystyrene high-fluorescence microsphere.

(2) Placing the polystyrene high-fluorescence microspheres in dimethylbenzene for swelling, adding concentrated sulfuric acid with the concentration of 98 wt%, reacting for 5 hours at the temperature of 100 ℃, and removing the solvent and the residual sulfuric acid to obtain sulfonated polystyrene high-fluorescence microspheres; wherein the mass ratio of the polystyrene high-fluorescence microspheres to the xylene is 1: 1.5; the mass ratio of the polystyrene high-fluorescence microspheres to the concentrated sulfuric acid with the concentration of 98 wt% is 1: 6;

(3) mixing the sulfonated polystyrene high-fluorescence microspheres with a sodium hydroxide solution with the concentration of 5 wt% (the volume ratio of the sulfonated polystyrene high-fluorescence microspheres to the sodium hydroxide solution is 1:5), reacting for 0.5h at the temperature of 30 ℃, washing with water with the volume being 10 times that of the microspheres to remove concentrated sulfuric acid, and drying at the temperature higher than the boiling point of xylene to remove residual xylene to obtain sulfonic acid functionalized polystyrene high-fluorescence microspheres;

the sulfonic acid functionalized polystyrene high-fluorescence microsphere is a polystyrene microsphere which takes 1, 7-vinyl-perylene imide derivative as a cross-linking agent and has sulfonic acid functional groups; the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 300nm, and the aperture variance is 1.6; the specific surface area is 800m²g^-1(ii) a The fluorescence quantum yield is 80%; the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit in the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 1: 4; the loading capacity of the sodium sulfonate functional group is 3 mmol/g;

(4) mixing 45 wt% of PET powder, 60 wt% of sulfonic acid functionalized polystyrene high-fluorescence microspheres, 10 wt% of calcium stearate and 5 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol; melting and extruding the components after 35min of mixing at 225 ℃ to prepare functional master batches of the fluorescent microspheres containing sulfonic acid functional groups;

Metering 30% of nylon fiber spinning melt, 70% of master batch added with fluorescent microspheres and pure polyester fiber melt according to the weight percentage (so that the mass percentage of the fluorescent microspheres in the polyester fiber is 10%); then the mixture is sent into a composite spinning box, and is sequentially spun through a distribution plate, a spinneret plate and the like of a spinning assembly in the box, and then is cooled, oiled and wound to form composite oriented yarn through measuring and blowing; the distribution plate is provided with eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the polyamide fibers to form a shape like a Chinese character 'mi', the aperture of each distribution hole is 30mm, and the width, depth and length of each distribution groove are 0.35mm, 0.32mm and 6mm in sequence. The temperature of the melt conveying pipeline is 275 ℃, the temperature of the spinning manifold is 275 ℃, the air speed of the side blowing is 0.8m/s, the temperature of the hot roller is 170 ℃, and the spinning speed is 3500 m/min.

The prepared superfine polyester fluorescent fiber with high adsorption function contains sulfonic acid functionalized polystyrene high-fluorescence microspheres; obtaining the filament number of 0.5dtex after opening; the maximum adsorption capacity reaches 170 mg/g; the high-adsorption superfine polyester fluorescent fiber has the elongation at break of 20 percent and the titer of composite fiber of 180 dtex.

Claims

1. A superfine polyester fluorescent fiber with high adsorption function is characterized in that: the polyester fluorescent fiber is a polyester fiber loaded with sulfonic acid functionalized polystyrene high-fluorescence microspheres; the mass percentage of the fluorescent microspheres in the polyester fiber is 7-10%, and the filament number obtained after fiber splitting is 0.20-0.50 dtex; the maximum adsorption capacity reaches 140-170 mg/g;

the load refers to that sulfonic acid functional groups are introduced into the polyester fibers by doping sulfonic acid functionalized polystyrene high-fluorescence microspheres, wherein the sulfonic acid functionalized polystyrene high-fluorescence microspheres are polystyrene microspheres taking 1, 7-vinyl-perylene imide derivatives as cross-linking agents; the polystyrene high-fluorescence microsphere is provided with a sulfonic acid functional group;

the 1, 7-vinyl-perylene bisimide derivative is a substituent with ethylene groups at 1,7 gulf position of perylene bisimide and an imide position of perylene bisimide is a bulky substituent;

the bulky substituent is sesquialter cage siloxane and/or long alkyl chain with side chain;

the silsesquioxane is

R is isobutyl or isooctyl;

the long alkyl chain with side chain is

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.

2. The superfine polyester fluorescent fiber with high adsorption function of claim 1, wherein the molar ratio of the 1, 7-vinyl-perylene imide derivative to the styrene structural unit is 1: 4-1: 3; the sulfonic acid functional group loading amount is 2.0 to 3.0 mmol/g.

3. The superfine polyester fluorescent fiber with high adsorption function as claimed in claim 1, wherein the mean diameter of the sulfonic acid functionalized polystyrene high-fluorescence microsphere is 100-300nm, and the pore size variance is 0.8-1.6; the specific surface area is 800-²g^-1(ii) a The yield of the fluorescence quantum is 60-80%.

4. The superfine polyester fluorescent fiber with high adsorption function as claimed in claim 1, wherein the elongation at break of the superfine polyester fluorescent fiber with high adsorption function is 20-38%, and the fineness of the composite fiber is 150-180 dtex.

5. The method for preparing the superfine polyester fluorescent fiber with high adsorption function as claimed in any one of claims 1 to 4, which is characterized in that: melting and extruding components which are mixed for 25-35min at the temperature of 220-225 ℃ by using 35-45 wt% of PET powder, 40-60 wt% of sulfonic acid functionalized polystyrene high-fluorescence microsphere, 5-10 wt% of calcium stearate and 1-5 wt% of 2, 4-di- (n-octylthiomethylene) -6-methylphenol to prepare functional master batch of the fluorescent microsphere containing the sulfonic acid functional group; feeding polyamide-6 or polyamide-66 into the screw separately for melting to obtain spinning melt of polyamide fiber; then, measuring 15-30% of the nylon fiber spinning melt, 70-85% of the master batch added with the fluorescent microspheres and the pure polyester fiber melt according to the weight percentage of the two obtained spinning melts, so that the fluorescent microspheres account for 7-10% of the mass of the polyester fiber; then sending the mixture into a composite spinning box, spinning the mixture by sequentially passing through a distribution plate and a spinneret plate of a spinning assembly in the box, cooling by blowing, oiling and winding to obtain composite oriented yarn; wherein the temperature of the melt conveying pipeline is 255-275 ℃, the temperature of the spinning manifold is 260-275 ℃, the lateral blowing air speed is 0.3-0.8m/s, the temperature of the hot roller is 130-17 ℃, and the spinning speed is 2500-3500 m/min; eight distribution holes for introducing the spinning melt of the polyester fibers and four distribution grooves for introducing the spinning melt of the polyamide fibers are formed on the distribution plate to form a shape like a Chinese character 'mi', the aperture of each distribution hole is 0.24-0.30mm, and the groove width, the groove depth and the groove length of each distribution groove are 0.3-0.35mm, 0.28-0.32mm and 5-6mm in sequence; finally false twisting and deforming the composite oriented yarn to obtain the fluorescent composite fiber product; and (3) obtaining the fluorescent superfine fiber on a liquid flow coloring agent through alkali decrement and mechanical fiber opening.

6. The preparation method of claim 5, wherein the polystyrene high-fluorescence microsphere adopts emulsion polymerization, and comprises the following steps:

(3) adding 1.5-10 wt% of sodium chloride demulsifier into the emulsion under the condition of stirring, coagulating, filtering, washing with hot water, and drying at the temperature higher than the boiling point of the pore-forming agent to obtain the polystyrene high-fluorescence microsphere.

7. The method according to claim 6, wherein the peroxide initiator is dibenzoyl oxide (BPO) or diethylhexyl dicarbonate oxide (EHP); the organic pore-making agent is toluene, and the mass ratio of the peroxide initiator to the styrene is 1: 75-85; the molar ratio of the styrene to the 1, 7-vinyl-perylene bisimide derivative is 3-4: 1; the mass ratio of the organic pore-forming agent to the styrene is 1: 1-4;

8. The method of claim 7, wherein the sulfonic acid functionalization treatment comprises:

the organic solvent is dichloroethane, toluene, xylene or tetrahydrofuran;

the concentration of the sodium hydroxide solution is 0.1-5 wt%;