CN111793842B

CN111793842B - Fluorescent brightening dark-color dyeable polypropylene fiber and preparation method thereof

Info

Publication number: CN111793842B
Application number: CN202010669461.3A
Authority: CN
Inventors: 顾益明; 孙宾; 黄新强; 朱美芳; 顾洪达; 陈龙; 陈珈
Original assignee: Changshu Polyester Co ltd; Donghua University
Current assignee: Changshu Polyester Co ltd; Donghua University
Priority date: 2020-07-13
Filing date: 2020-07-13
Publication date: 2022-06-17
Anticipated expiration: 2040-07-13
Also published as: CN111793842A

Abstract

The invention relates to a fluorescent brightening dark dyeable polypropylene fiber and a preparation method thereof, wherein the method comprises the steps of uniformly mixing polypropylene and polyacrylic acid microspheres (prepared by taking 1, 7-vinyl-perylene imide derivatives as a cross-linking agent), drying, and then putting into a double-screw extruder for extrusion to prepare master batches; and finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain the fluorescent brightening dark-color dyeable polypropylene fiber, wherein the prepared fiber generates a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene imide derivative under the excitation of a wavelength of 440-460 nm, the fluorescence quantum yield is 95-99%, and the dyeing performance is as follows: dyeing with cationic yellow X-8GL at 125 ℃, wherein the dye uptake is 65-95%; the dyeing K/S value is 11.41-12.70; the method of the invention can obtain the polypropylene fiber with bright and bright color by selecting the common cationic coloring agent.

Description

Fluorescent brightening dark-color dyeable polypropylene fiber and preparation method thereof

Technical Field

The invention belongs to the technical field of polypropylene fibers, and relates to a fluorescent brightening dark-colored dyeable polypropylene fiber and a preparation method thereof.

Background

In recent years, in the field of textile clothing, with the increasing demand of people for colors, there is a demand for bright and vivid clothing fabrics. The fluorescent dye belongs to a special functional dye, has the coloring characteristic of the conventional dye and can emit fluorescence, so that the saturation and the vividness of the fabric dyed by the fluorescent dye are relatively higher compared with those of the common dye. Fluorescent dyes are now widely used in various industries such as textile, plastic dyeing, printing pigments, etc., for example: eye-catching marks on the clothes of traffic policemen and cleaners, high-grade umbrellas, bags, sports clothes, ties, outdoor decorative materials and the like. With the advance of science and technology, fluorescent dyes are also gradually applied to high-end fields such as biology, medicine and the like.

Fluorescent dyes exhibit brighter colors than non-fluorescent dyes, increasing the saturation and vividness of the fabric. However, the types of fluorescent dyes currently applied to fabrics are not many, and most of the fluorescent dyes are mainly applied to synthetic fibers such as polyester fibers because a large part of the fluorescent dyes cannot be firmly combined with the fibers. The most widely used fluorescent whitening agent for cotton fabrics. The fluorescent whitening agent absorbs invisible ultraviolet light in human eyes, emits extremely bright and gorgeous bluish violet light, and improves the whiteness and the vividness of the fabric. Patent CN106758386A discloses a processing technology of fluorescent polyester fabric, which comprises the steps of refining treatment, dyeing and finishing and post-treatment; wherein the dyeing finishing is to carry out co-bath on the fabric to be dyed and the dyeing working solution by adopting a one-bath method, the bath ratio is 1:10, the temperature is increased to 60 ℃, the temperature increase rate is 5 ℃/min, the temperature is kept for 40-50 minutes, the temperature is continuously increased to 120 ℃, the temperature increase rate is 1 ℃/min, the temperature is kept for 30-40 minutes, and the dyeing is finished. The fluorescent polyester fabric can be worn daily to meet the requirement of fashion, and can be matched with 3M reflecting materials purchased in the market at will according to the requirement, so that the high-visibility warning clothing which can be used at night is manufactured, and the fluorescent performance of the fluorescent polyester fabric meets the requirement of related standards.

Polypropylene fibers, named polypropylene fibers, can be classified into long fibers, short fibers, spun-bonded nonwoven fabrics, melt-blown nonwoven fabrics, and the like, and have a wide range of applications. But polypropylene molecular chains do not contain polar groups or reactive groups, so that the polypropylene molecular chains are very strong in hydrophobicity and lack affinity to general dyes; meanwhile, because the polypropylene fiber has high crystallinity (the higher the crystallinity, the higher the proportion of isotactic substances and syndiotactic substances), the structure is quite compact, so that dye molecules are difficult to diffuse into the polypropylene fiber, and the polypropylene fiber is the most difficult to dye in the existing synthetic fiber. In order to meet the production and application requirements and improve the coloring property of polypropylene fibers, a great deal of work is done by many experts and scholars at home and abroad, and various methods for coloring polypropylene fibers are proposed. In the prior art, polypropylene fibers are treated by low-temperature plasma in the air and then dyed by Ostalan brown BL Supra and Alizarine Chrome red G, so that the dyeability is high, and the mechanical friction fastness and the washing fastness are high.

In order to improve the dyeing performance of polypropylene fiber and better meet the printing and dyeing requirements, the polypropylene fiber must be modified to meet at least the following two conditions: the compact structure of the fiber is changed, so that the dye is easy to permeate into the fiber matrix; a certain number of polar groups having a sufficiently large affinity for the dye are introduced into the fiber matrix. At present, the dyeable polypropylene fibers prepared by a modification method at home and abroad are mainly as follows 5 types: a method of modifying by blending a metal compound; blending heterogeneous polymer modification method; graft copolymerization modification; composite fiber method and fiber surface treatment method. In China, many researches on dyeing of polypropylene fibers are carried out, for example, Anhui Tanbao textile technology Co., Ltd provides a cationic modified dyeing method for polypropylene fibers, which comprises the following steps: modifying fibers, pretreating, pre-shaping gray fabric, reducing and cleaning, preparing dye liquor, dyeing and post-treating. The dyeing process has the advantages of less steps, short dyeing time, recyclable dye after dyeing and reduced environmental pollution. The dyeing method of modifying polypropylene fiber or fabric by using low-temperature plasma graft polymerization method of China science nanotechnology engineering center Limited company is characterized by that in the course of plasma treatment the monomer of acrylic acid or monomer solution of acrylic acid is introduced or the monomer solution of acrylic acid is used to graft on the surface of polypropylene fiber or fabric the dyeing seat which is favorable for dyeing and promoting deep dyeing so as to make the polypropylene fiber or fabric treated by said method can be dyed by adopting "normal-temp. boiling dyeing" process.

Disclosure of Invention

Aiming at the problems that fluorescent dyes are used for dyeing bright colors or high-brightness polypropylene fibers in the prior art, and the selection of the types of the dyes has limitation, carboxyl functionalized high-fluorescence polyacrylic microspheres are blended in a polypropylene matrix to enhance the combination of the fibers and cationic dyes, and the crystallinity of the polypropylene is damaged by the addition of the microspheres, so that the dyes can enter the polypropylene matrix easily, and the deep color of the polypropylene fibers can be dyed. And because the emission wavelength of the perylene bisimide in the fluorescent microsphere is overlapped with the complementary color wavelength of the absorption wavelength of the fiber cationic coloring agent, the fluorescent brightening dark-colored dyeable polypropylene fiber with deep and bright color can be obtained.

The invention aims to provide a fluorescent brightening dark-color dyeable polypropylene fiber which mainly comprises a polypropylene matrix and polyacrylic acid microspheres dispersed in the polypropylene matrix; the fluorescence brightening dark-color dyeable polypropylene fiber generates a characteristic fluorescence emission peak of 630-645nm 1, 7-vinyl-perylene imide derivatives under the excitation of the wavelength of 440-460 nm.

The invention also aims to provide a preparation method of the fluorescent brightening dark-color dyeable polypropylene fiber, which comprises the steps of uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting the mixture into a double-screw extruder for extrusion to prepare master batches; and finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain the fluorescent brightening dark-color dyeable polypropylene fiber.

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

a fluorescent brightening dark-color dyeable polypropylene fiber mainly comprises a polypropylene matrix and polyacrylic acid microspheres dispersed in the polypropylene matrix; the fluorescence brightening dark-color dyeable polypropylene fiber generates a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene bisimide derivative under the excitation of the wavelength of 440-460 nm, and the color is orange yellow;

the polyacrylic acid microsphere is a polyacrylic acid microsphere taking 1, 7-vinyl-perylene bisimide derivatives as a cross-linking agent;

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.

The 1, 7-vinyl-perylene imide derivatives in the present invention function as: the perylene imide derivative with the bulky imide site substitution can enable the molecules to have great steric hindrance when being aggregated through pi-pi interaction, and the molecules can be more easily present in a system in a single-molecule state in the presence of a solvent, and crosslinking points are more uniformly present in the microspheres. The 1, 7-vinyl-perylene bisimide derivative also has fluorescence performance, and the amount of the added perylene bisimide derivative is far less than that of carboxyl on the microsphere, so that the color of the perylene bisimide has little influence on the color of the dark dyeable fiber. Meanwhile, the fiber produced by blending the polyacrylic acid microspheres has fluorescence emission, and the emission wavelength of the perylene bisimide is overlapped with the complementary color wavelength of the absorption wavelength of the specific cationic dye, so that the deep and bright fluorescence brightening dark dyeable polypropylene fiber can be obtained, and the fiber can be dyed more brightly and brightly;

as a preferred technical scheme:

the fluorescent brightening dark-color dyeable polypropylene fiber is characterized in that the bulky substituent is sesqui-cage-shaped 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 linkage position of the chemical bond isAn 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.

The fluorescent brightening dark-color dyeable polypropylene fiber has the advantages that the molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit is 14-21.5: 125. Because the addition amount of the 1, 7-vinyl-perylene imide derivative is far less than that of acrylic acid, the number of dye sites in the fiber is large, and the influence of fluorescence on dyeing is small.

According to the fluorescent brightening dark-color dyeable polypropylene fiber, the average diameter of the polyacrylic acid microspheres is 150-300 nm, the average pore diameter is 10-30 nm, the porosity is 35-55%, the fluorescence quantum yield is 95-99%, a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene imide derivative is generated under excitation of a wavelength of 440-460 nm, and the color is orange yellow.

The fluorescent brightening dark-color dyeable polypropylene fiber has the advantages that the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.09-3.9 cN/dtex, the elongation at break is 17.73-26.6%, and the melting point is 150-180 ℃; the crystallinity is reduced after blending, and conditions are created for dyeing; the yield of the fluorescence quantum is 95-99%;

the dyeing performance of the fluorescent brightening dark-color dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 deg.C, dye-uptake is 65-95%, and color is bright and uniform; the dyeing K/S value is 11.41-12.70; the dye uptake of the cation yellow X-8GL is increased along with the increase of the temperature, the dye uptake is the highest when the temperature reaches 120-130 ℃, the dye uptake is not obviously changed when the dyeing temperature is increased,

the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grades, white cloth is stained with 3-5 grades, and rubbing fastness is as follows: dry 4-5 grade, wet 3-5 grade, color fastness to perspiration: original color change is 4-5 grades, white cloth is stained with 4-5 grades, and sublimation color fastness is as follows: changing the color of the original sample to 4-5 grades, and staining the white cloth to 4-5 grades;

the reflectivity of the fabric made of the fluorescent brightening dark-color dyeable polypropylene fiber is 95-145%, and the chromaticity coordinate value of the dyed fabric is as follows: x is 0.45-0.5, y is 0.42-0.52, and the yellow region is located;

the dyeing process of the cationic yellow X-8GL is as follows:

(1) placing the fluorescent brightening dark-color dyeable polypropylene fiber in a dyeing bath, adding water according to a bath ratio of l: 20-50 by weight, adding 0.05-2% of dissolved dye cation yellow X-8GL, 0.3-2% of leveling agent 1277, 0-10% of anhydrous sodium sulphate and 0.5-2% of acetic acid, and running for 10-20 min at 5-25 ℃;

the anhydrous sodium sulphate and the acetic acid are added according to the weight of the blended polypropylene.

(2) Heating to 50-80 ℃ at the speed of 0.5-4 ℃/min, and then running for 10-30 min;

(3) heating to 95-100 ℃ at the speed of 1-2 ℃/min, and running for 30-60 min;

(4) and (3) reducing the temperature to 35-45 ℃ at the speed of 2-4 ℃/min, discharging residual liquid, washing with clear water at the temperature of 20-40 ℃, and drying or performing functional finishing by adopting a method known in the art.

The invention also provides a preparation method of the fluorescent brightening dark-color dyeable polypropylene fiber, which comprises the steps of adding the polypropylene and the polyacrylic acid microspheres into a stirrer, uniformly stirring and mixing, drying (the drying temperature is 160-180 ℃ and the drying time is 30-60 min), and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment, adjusting parameters of different positions of the production equipment, and spinning to obtain the fluorescent brightening dark-color dyeable polypropylene fiber;

the preparation method of the high-fluorescence polyacrylic acid microsphere 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 imide 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 the polyacrylate microsphere with sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain the high-fluorescence polyacrylic microsphere (solid powder).

As a preferred technical scheme:

in the method, the screw rotating speed of the double-screw extruder (TSE-3Q) is 150-200 r/min, and the screw temperature is 200-220 ℃; the screws which rotate reversely of the double-screw extruder are arranged in parallel in the cavity of the 8-shaped extrusion cage with different sizes and apertures along the longitudinal direction, the screws are completely meshed in the feeding section and are not meshed in the main base section, and the extrusion cage is divided into 4 sections of grain outlet holes with different yarn outlet gaps along the longitudinal direction;

in the master batch, by weight, 80-120 parts of polypropylene and 40-60 parts of polyacrylic acid microspheres are added; in the spinning process, the addition amount of the master batch is 7-8 wt%;

the spinning process parameters are as follows: the temperature of the melt conveying pipeline is 200-260 ℃, the temperature of the melt filter is 220-260 ℃, the temperature of the spinning manifold is 220-260 ℃, the air speed of the side blowing is 0.5-0.7 m/s, the air temperature is 15 +/-2 ℃, the temperature of the hot roll is 110 +/-10 ℃, the spinning speed is 2500-2800 m/min, and the winding angle is 7-8 degrees. With the increase of the spinning speed, the tension in the spinning process is continuously increased, the fiber strength is increased, the elongation is reduced, but the crystallinity and the orientation thereof reach saturation at the spinning speed of 2500 m/min.

The method as described above, wherein the emulsifier is potassium laurate, sodium lauryl sulfate or sodium dioctyl sulfosuccinate; the organic solvent is toluene or xylene.

According to the method, 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 methyl acrylate is 4-6 wt%, the content of 1, 7-vinyl-perylene bisimide derivatives is 9-15 wt%, and the content of organic solvents is 6-10 wt%; t2 is 75-95 ℃;

in the step (3), the mass fraction of the potassium persulfate is 0.06-0.12% of the acrylate dispersion liquid; the stirring speed is 300-500 r/min, and the stirring time is 15-35 min; 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 ℃.

The principle of the invention is as follows:

the invention adopts 1, 7-vinyl-perylene imide derivatives as crosslinking points to prepare polyacrylate microspheres, and then hydrolyzes polyacrylate into polyacrylic acid to obtain the polyacrylic acid microspheres. The polyacrylic acid microsphere has a porous structure and a large specific surface area, and can expose more reactive carboxyl groups. Because the polypropylene fiber structure has no polar group, the fiber structure is compact and difficult to dye. Since many dyes carry cationic groups, if carboxyl groups are carried in the cationic groups and the matrix, electrostatic interactions between the carboxyl groups and the cations occur, increasing the interaction of the cationic dye with the matrix. Therefore, the polyacrylic acid microspheres with carboxyl groups are added in the production process of the polypropylene fibers, polar carboxyl groups are introduced into the polypropylene fibers, and the combination of the fibers and the cationic dye is enhanced. And the polyacrylic acid microspheres are porous, exposed polar carboxyl groups are added on the microsphere structure, and dyeing seats are further added. Meanwhile, the polyacrylic acid main chain structures of the polypropylene and the polyacrylic acid microspheres are similar, so that the polyacrylic acid microspheres are well dispersed in the polypropylene slices and the polypropylene fibers (the dispersion is mainly the problem between a microsphere matrix and a fiber matrix, and the influence of a cross-linking agent is small), and the influence on the mechanical property of the fibers is small.

The perylene bisimide derivative also has fluorescence property, and the amount of the added perylene bisimide derivative is far less than the amount of carboxyl on the microsphere, so that the color of the perylene bisimide has little influence on the color of the dark dyeable fiber. And because the emission wavelength of the perylene bisimide is overlapped with the complementary color wavelength of the absorption wavelength of the specific cationic coloring agent, the deep and bright fluorescent brightening dark dyeable polypropylene fiber can be obtained, so that the fiber can be dyed more brightly and can be comparable to the effect of a fluorescent dye. Thus, polypropylene fibers which are deep dyeable and have a bright and vivid color can be obtained.

Has the advantages that:

(1) the fluorescent brightening dark-color dyeable polypropylene fiber can be deeply dyed and has high brightness and bright color;

(2) according to the preparation method of the fluorescent brightening dark-colored dyeable polypropylene fiber, a fluorescent coloring agent is not needed, and a common cationic coloring agent can be selected to obtain the polypropylene fiber with bright and bright color.

Detailed Description

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

Example 1

The preparation method of the 1, 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 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 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 was closely focused on color change 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 15.00mL of 1-methyl-2-pyrrolidone (NMP) 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 is finishedAfter cooling to room temperature, 120.00mL of methanol was added thereto, and the mixture was stirred 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.

(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.

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 show 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

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 middle lower layer of the separating funnel is an organic phase, the upper layer is a water phase, the organic phase is purple red, and the water phase is pink. And (3) spin-drying the extracted trichloromethane solution to obtain a 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 large-volume substituent access method comprises the following steps:

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

(0.50g,0.91mmol) and 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

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

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. 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 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

(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.

Example 7

A preparation method of fluorescent brightening dark-color dyeable polypropylene fiber comprises the following steps:

(1) preparing polyacrylic acid microspheres:

(1.1) mixing potassium laurate and deionized water at a temperature of 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%, 1, 7-vinyl-

The content of the perylene bisimide derivative is 13.6 weight percent, the content of toluene is 10 weight percent, and the content of potassium laurate is 0.4 weight percent;

(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 mass fraction of the potassium persulfate is 0.06 percent of the acrylic ester 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, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres; wherein the concentration of the sodium hydroxide ethanol solution is 1mol/L, and 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 average diameter of the prepared polyacrylic acid microsphere is 150nm, the average pore diameter is 10nm, the porosity is 35%, the fluorescence quantum yield is 95%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645nm is generated under excitation of the wavelength of 440-460 nm;

(2) preparing the fluorescent brightening dark-color dyeable polypropylene fiber:

firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber; wherein the screw rotating speed of the double-screw extruder is 150r/min, and the screw temperature is 200 ℃; in the master batch, by weight, 80 parts of polypropylene and 40 parts of polyacrylic acid microspheres are added; in the spinning process, the addition amount of the master batch is 7 wt%; the molecular weight of the polypropylene is 146200, the molecular weight distribution index is 2.5, and the melt index is 10g/10 min;

the spinning process parameters are as follows: the temperature of a melt conveying pipeline is 200 ℃, the temperature of a melt filter is 220 ℃, the temperature of a spinning manifold is 220 ℃, the side blowing air speed is 0.5m/s, the air temperature is 13 ℃, the temperature of a hot roller is 100 ℃, the spinning speed is 2500m/min, and the winding angle is 7 degrees.

The molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit in the finally prepared fluorescent brightening dark dyeable polypropylene fiber is 14: 125; the yield of fluorescence quantum of the fluorescent brightening dark-color dyeable polypropylene fiber is 95%, and a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.09cN/dtex, the elongation at break is 26.6 percent, and the melting point is 150 ℃; the dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 deg.C with dye uptake of 65%; the dyeing K/S value is 11.41; the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grades, white cloth is stained with 3 grades, and rubbing fastness is as follows: dry 4 grade, wet 3 grade, perspiration color fastness: original color change 4 grade, white cloth staining 4 grade, sublimation color fastness: changing color of the original sample by 4 grades, and staining white cloth by 4 grades; the fabric reflectivity is 95%, and the chromaticity coordinate value of the dyed fabric is as follows: x is 0.45 and y is 0.42.

Example 8

(1) preparing polyacrylic acid 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 derivatives 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 mass fraction of the potassium persulfate is 0.07 percent of the acrylate dispersion liquid, the polymerization time is 5 hours, and the polymerization temperature is 84 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres; wherein the concentration of the sodium hydroxide ethanol solution is 1mol/L, and 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 101 ℃;

the average diameter of the prepared polyacrylic acid microsphere is 207nm, the average pore diameter is 27nm, the porosity is 50%, the fluorescence quantum yield is 97%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645nm is generated under excitation of the wavelength of 440-460 nm;

firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber; wherein the screw rotating speed of the double-screw extruder is 159r/min, and the screw temperature is 208 ℃; in the master batch, by weight, 117 parts of polypropylene and 41 parts of polyacrylic acid microspheres are added; in the spinning process, the addition amount of the master batch is 7 wt%; the molecular weight of the polypropylene is 146300, the molecular weight distribution index is 2.6, and the melt index is 17g/10 min;

the spinning process parameters are as follows: the temperature of a melt conveying pipeline is 241 ℃, the temperature of a melt filter is 220 ℃, the temperature of a spinning manifold is 233 ℃, the speed of a side blowing air is 0.5m/s, the air temperature is 14 ℃, the temperature of a hot roller is 114 ℃, the spinning speed is 2569m/min, and the winding angle is 7 degrees.

The molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit in the finally prepared fluorescent brightening dark dyeable polypropylene fiber is 16: 125; the fluorescence quantum yield of the fluorescent brightening dark-color dyeable polypropylene fiber is 97%, and a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene bisimide derivative is generated under the excitation of the wavelength of 440-460 nm; the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.2cN/dtex, the elongation at break is 24.36 percent, and the melting point is 179 ℃; the dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 deg.C, dye uptake is 67%; the dyeing K/S value is 11.56; the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grades, white cloth is stained with 3 grades, and rubbing fastness is as follows: dry 4, wet 4, perspiration color fastness: original color change 4 grade, white cloth staining 4 grade, sublimation color fastness: original color change is 4 grades, and white cloth is stained with 4 grades; the fabric reflectance was 138%, and the chromaticity coordinate values of the dyed fabric were: x is 0.46 and y is 0.47.

Example 9

(1) preparing polyacrylic acid 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 mass fraction of the potassium persulfate is 0.06 percent of the acrylic ester dispersion liquid, the polymerization time is 8h, and the polymerization temperature is 78 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres; wherein the concentration of the sodium hydroxide ethanol solution is 1mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1.2; the heating reflux time is 9h, and the drying temperature is 106 ℃;

the average diameter of the prepared polyacrylic acid microsphere is 235nm, the average pore diameter is 19nm, the porosity is 53%, the fluorescence quantum yield is 99%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645nm is generated under excitation of the wavelength of 440-460 nm;

firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber; wherein the screw rotating speed of the double-screw extruder is 200r/min, and the screw temperature is 202 ℃; in the master batch, by weight, 120 parts of polypropylene and 51 parts of polyacrylic acid microspheres are added; in the spinning process, the addition amount of the master batch is 7 wt%; the molecular weight of the polypropylene is 148800, the molecular weight distribution index is 2.8, and the melt index is 18g/10 min;

the spinning process parameters are as follows: the temperature of a melt conveying pipeline is 205 ℃, the temperature of a melt filter is 228 ℃, the temperature of a spinning manifold is 257 ℃, the air speed of a side blowing air is 0.6m/s, the air temperature is 15 ℃, the temperature of a hot roller is 107 ℃, the spinning speed is 2584m/min, and the winding angle is 7 degrees.

The molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit in the finally prepared fluorescent brightening dark dyeable polypropylene fiber is 20: 125; the yield of fluorescence quantum of the fluorescent brightening dark-color dyeable polypropylene fiber is 96%, and a characteristic fluorescence emission peak of 630-645nm of 1, 7-vinyl-perylene bisimide derivatives is generated under the excitation of the wavelength of 440-460 nm; the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.46cN/dtex, the elongation at break is 19.45 percent, and the melting point is 172 ℃; the dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 deg.C, dye uptake is 95%; the dyeing K/S value is 11.48; the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grades, white cloth is stained with 5 grades, and rubbing fastness is as follows: dry 5, wet 5, perspiration color fastness: original color change is 4 grades, white cloth is stained with 5 grades, and sublimation color fastness is as follows: changing color of the original sample by 4 grades, and staining white cloth by 5 grades; the fabric reflectance was 140%, and the chromaticity coordinate values of the dyed fabric were: x is 0.48 and y is 0.52.

Example 10

(1) preparing polyacrylic acid 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 mass fraction of the potassium persulfate is 0.08 percent of the acrylic ester dispersion liquid, the polymerization time is 8h, and the polymerization temperature is 81 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres; wherein the concentration of the sodium hydroxide ethanol solution is 1.5mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 2; heating and refluxing for 9h, and drying at 105 deg.C;

the average diameter of the prepared polyacrylic acid microsphere is 201nm, the average pore diameter is 21nm, the porosity is 48%, the fluorescence quantum yield is 98%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645nm is generated under excitation of the wavelength of 440-460 nm;

firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber; wherein the screw rotating speed of the double-screw extruder is 170r/min, and the screw temperature is 206 ℃; in the master batch, 87 parts of polypropylene and 57 parts of polyacrylic acid microspheres are calculated according to parts by weight; in the spinning process, the addition amount of the master batch is 8 wt%; the molecular weight of the polypropylene is 149200, the molecular weight distribution index is 3.2, and the melt index is 12g/10 min;

the spinning process parameters are as follows: the temperature of a melt conveying pipeline is 205 ℃, the temperature of a melt filter is 246 ℃, the temperature of a spinning box body is 231 ℃, the air speed of a side blowing air is 0.6m/s, the air temperature is 17 ℃, the temperature of a hot roller is 108 ℃, the spinning speed is 2790m/min, and the winding angle is 8 degrees.

The molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit in the finally prepared fluorescent brightening dark dyeable polypropylene fiber is 21.5: 125; the fluorescence quantum yield of the fluorescent brightening dark-color dyeable polypropylene fiber is 98%, and a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.9cN/dtex, the elongation at break is 17.73%, and the melting point is 169 ℃; the dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 deg.C with dye uptake of 71%; the dyeing K/S value is 12.70; the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grades, white cloth is stained with 4 grades, and rubbing fastness is as follows: dry 4, wet 4, perspiration color fastness: original color change 4 grade, white cloth staining 4 grade, sublimation color fastness: original color change is 4 grades, and white cloth is stained with 4 grades; the fabric reflectance was 107%, and the chromaticity coordinate values of the dyed fabric were: x is 0.5 and y is 0.52.

Example 11

(1) preparing polyacrylic acid 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 mass fraction of the potassium persulfate is 0.08 percent of the acrylate dispersion liquid, the polymerization time is 7h, and the polymerization temperature is 89 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres; wherein the concentration of the sodium hydroxide ethanol solution is 2mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 2.2; the heating reflux time is 11h, and the drying temperature is 94 ℃;

the average diameter of the prepared polyacrylic acid microsphere is 290nm, the average pore diameter is 17nm, the porosity is 55%, the fluorescence quantum yield is 98%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645nm is generated under excitation of the wavelength of 440-460 nm;

firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber; wherein the screw rotating speed of the double-screw extruder is 172r/min, and the screw temperature is 202 ℃; in the master batch, 94 parts of polypropylene and 57 parts of polyacrylic acid microspheres are calculated according to parts by weight; in the spinning process, the addition amount of the master batch is 7 wt%; the molecular weight of the polypropylene is 150000, the molecular weight distribution index is 3.1, and the melt index is 12g/10 min;

the spinning process parameters are as follows: the temperature of a melt conveying pipeline is 237 ℃, the temperature of a melt filter is 238 ℃, the temperature of a spinning box body is 221 ℃, the air speed of a side blowing air is 0.6m/s, the air temperature is 13 ℃, the temperature of a hot roller is 106 ℃, the spinning speed is 2688m/min, and the winding angle is 8 degrees.

The molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit in the finally prepared fluorescent brightening dark dyeable polypropylene fiber is 14.5: 125; the fluorescence quantum yield of the fluorescent brightening dark-color dyeable polypropylene fiber is 98%, and a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.6cN/dtex, the elongation at break is 25.12 percent, and the melting point is 176 ℃; the dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 deg.C, dye uptake is 90%; the dyeing K/S value is 11.89; the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grade, white cloth is stained with 5 grade, and rubbing fastness is as follows: dry 5, wet 4, perspiration color fastness: original color change is 4 grade, white cloth is stained with 5 grade, sublimation color fastness is as follows: changing color of 5 grades and staining white cloth of 4 grades; the fabric reflectivity is 96%, and the chromaticity coordinate value of the dyed fabric is as follows: x is 0.45 and y is 0.49.

Example 12

(1) preparing polyacrylic acid 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 bisimide derivative (prepared in example 2) in toluene, adding the mixture into the system I, and mixing at the 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 mass fraction of the potassium persulfate is 0.12 percent of the acrylic ester 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, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres; wherein the concentration of the sodium hydroxide ethanol solution is 2mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 2.8; the heating reflux time is 11h, and the drying temperature is 96 ℃;

the average diameter of the prepared polyacrylic acid microsphere is 288nm, the average pore diameter is 25nm, the porosity is 47%, the fluorescence quantum yield is 97%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645nm is generated under excitation of the wavelength of 440-460 nm;

firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber; wherein the screw rotating speed of the double-screw extruder is 188r/min, and the screw temperature is 216 ℃; in the master batch, 96 parts of polypropylene and 40 parts of polyacrylic acid microspheres are calculated according to parts by weight; in the spinning process, the addition amount of the master batch is 7 wt%; the molecular weight of the polypropylene is 149500, the molecular weight distribution index is 4, and the melt index is 16g/10 min;

the spinning process parameters are as follows: the temperature of a melt conveying pipeline is 237 ℃, the temperature of a melt filter is 229 ℃, the temperature of a spinning box body is 241 ℃, the air speed of a side blowing is 0.7m/s, the air temperature is 15 ℃, the temperature of a hot roller is 116 ℃, the spinning speed is 2707m/min, and the winding angle is 7 degrees.

The molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit in the finally prepared fluorescent brightening dark dyeable polypropylene fiber is 14.3: 125; the fluorescence quantum yield of the fluorescent brightening dark-color dyeable polypropylene fiber is 96%, and a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene bisimide derivative is generated under excitation of a wavelength of 440-460 nm; the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.8cN/dtex, the elongation at break is 25.98 percent, and the melting point is 153 ℃; the dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 deg.C, dye uptake is 66%; the dyeing K/S value is 12.34; the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grades, white cloth is stained with 3 grades, and rubbing fastness is as follows: dry 4 grade, wet 3 grade, perspiration color fastness: original color change 4 grade, white cloth staining 4 grade, sublimation color fastness: original color change is 4 grades, and white cloth is stained with 4 grades; the fabric reflectance was 115%, and the chromaticity coordinate values of the dyed fabric were: x is 0.49 and y is 0.46.

Example 13

(1) preparing polyacrylic acid 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 mass fraction of the potassium persulfate is 0.07 percent of the acrylate dispersion liquid, the polymerization time is 7h, and the polymerization temperature is 93 ℃;

(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres; wherein the concentration of the sodium hydroxide ethanol solution is 2mol/L, and 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 109 ℃;

the average diameter of the prepared polyacrylic acid microsphere is 290nm, the average pore diameter is 19nm, the porosity is 50%, the fluorescence quantum yield is 99%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645nm is generated under excitation of the wavelength of 440-460 nm;

firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber; wherein the screw rotating speed of the double-screw extruder is 150r/min, and the screw temperature is 217 ℃; in the master batch, 108 parts of polypropylene and 44 parts of polyacrylic acid microspheres are calculated according to parts by weight; in the spinning process, the addition amount of the master batch is 8 wt%; the molecular weight of the polypropylene is 150200, the molecular weight distribution index is 3.7, and the melt index is 17g/10 min;

the spinning process parameters are as follows: the temperature of the melt conveying pipeline is 243 ℃, the temperature of the melt filter is 241 ℃, the temperature of the spinning box body is 239 ℃, the side blowing air speed is 0.7m/s, the air temperature is 14 ℃, the temperature of the hot roll is 117 ℃, the spinning speed is 2748m/min, and the winding angle is 7 degrees.

The molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit in the finally prepared fluorescent brightening dark dyeable polypropylene fiber is 15: 125; the yield of fluorescence quantum of the fluorescent brightening dark-color dyeable polypropylene fiber is 95%, and a characteristic fluorescence emission peak of 630-645nm of 1, 7-vinyl-perylene bisimide derivatives is generated under the excitation of the wavelength of 440-460 nm; the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.87cN/dtex, the elongation at break is 24.3 percent, and the melting point is 164 ℃; the dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 deg.C, dye uptake is 74%; the dyeing K/S value is 12.23; the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grades, white cloth is stained with 4 grades, and rubbing fastness is as follows: dry 4, wet 4, perspiration color fastness: original color change is 4 grade, white cloth is stained with 4 grade, sublimation color fastness is as follows: original color change is 4 grades, and white cloth is stained with 4 grades; the fabric reflectance was 105%, and the chromaticity coordinate values of the dyed fabric were: x is 0.49 and y is 0.42.

Example 14

(1) preparing polyacrylic acid 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 mass fraction of the potassium persulfate is 0.12 percent of the acrylic ester 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, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres; wherein the concentration of the sodium hydroxide ethanol solution is 2mol/L, and 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 average diameter of the prepared polyacrylic acid microsphere is 300nm, the average pore diameter is 30nm, the porosity is 55%, the fluorescence quantum yield is 99%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645nm is generated under excitation of the wavelength of 440-460 nm;

firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber; wherein the screw rotating speed of the double-screw extruder is 200r/min, and the screw temperature is 220 ℃; in the master batch, by weight, 120 parts of polypropylene and 60 parts of polyacrylic acid microspheres are added; in the spinning process, the addition amount of the master batch is 8 wt%; the molecular weight of the polypropylene is 150700, the molecular weight distribution index is 4.5, and the melt index is 20g/10 min;

the spinning process parameters are as follows: the temperature of a melt conveying pipeline is 260 ℃, the temperature of a melt filter is 260 ℃, the temperature of a spinning manifold is 260 ℃, the speed of a side blowing air is 0.7m/s, the air temperature is 17 ℃, the temperature of a hot roller is 120 ℃, the spinning speed is 2800m/min, and the winding angle is 8 degrees.

The molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit in the finally prepared fluorescent brightening dark dyeable polypropylene fiber is 21: 125; the yield of fluorescence quantum of the fluorescent brightening dark-color dyeable polypropylene fiber is 99%, and a characteristic fluorescence emission peak of 630-645nm of 1, 7-vinyl-perylene bisimide derivatives is generated under the excitation of the wavelength of 440-460 nm; the breaking strength of the fluorescent brightening dark-color dyeable polypropylene fiber is 3.5cN/dtex, the elongation at break is 20.8 percent, and the melting point is 180 ℃; the dyeing performance of the fluorescent brightening dark dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 ℃ with dye uptake of 95%; the dyeing K/S value is 12.70; the color fastness of dyeing is as follows: soaping fastness: original color change is 4 grades, white cloth is stained with 5 grades, and rubbing fastness is as follows: dry 5, wet 4, perspiration color fastness: original color change 5 grade, white cloth staining 5 grade, sublimation color fastness: changing color of 5 grades in original state, and staining white cloth with 5 grades; the fabric reflectivity was 145%, and the chromaticity coordinate values of the dyed fabric were: x is 0.45 and y is 0.52.

Claims

1. A fluorescent brightening dark dyeable polypropylene fiber is characterized in that: mainly comprises a polypropylene matrix and polyacrylic microspheres dispersed in the polypropylene matrix; the fluorescent brightening dark-color dyeable polypropylene fiber generates a characteristic fluorescence emission peak of a 630-645nm 1, 7-vinyl-perylene bisimide derivative under excitation of a wavelength of 440-460 nm;

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

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;

2. The fluorescent brightening dark-colored dyeable polypropylene fiber according to claim 1, wherein the molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit is 14-21.5: 125.

3. The fluorescent brightening dark-colored dyeable polypropylene fiber according to claim 1, wherein the polyacrylic acid microspheres have an average diameter of 150-300 nm, an average pore diameter of 10-30 nm, a porosity of 35-55%, and a fluorescence quantum yield of 95-99%, and generate a characteristic fluorescence emission peak of 630-645nm of 1, 7-vinyl-perylene imide derivatives under excitation of a wavelength of 440-460 nm.

4. The fluorescent brightening dark-color dyeable polypropylene fiber according to claim 1, wherein the fluorescent brightening dark-color dyeable polypropylene fiber has a breaking strength of 3.09-3.9 cN/dtex, an elongation at break of 17.73-26.6% and a melting point of 150-180 ℃; the yield of the fluorescence quantum is 95-99%;

the dyeing performance of the fluorescent brightening dark-color dyeable polypropylene fiber is as follows: dyeing with cationic yellow X-8GL at 125 ℃, wherein the dye-uptake is 65-95%; the dyeing K/S value is 11.41-12.70;

the reflectivity of the fabric is 95-145%, and the chromaticity coordinate value of the dyed fabric is as follows: x is 0.45 to 0.5, and y is 0.42 to 0.52.

5. The method for preparing the fluorescent brightening dark-colored dyeable polypropylene fiber as claimed in any one of claims 1 to 4, which is characterized in that: firstly, uniformly mixing polypropylene and polyacrylic acid microspheres, drying, and then putting into a double-screw extruder for extrusion to prepare master batches; finally, adding the master batch into polypropylene melt spinning production equipment for spinning to obtain fluorescent brightening dark-color dyeable polypropylene fiber;

the preparation method of the polyacrylic acid microspheres comprises the following steps:

(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, 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 the polyacrylate microspheres with a sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres.

6. The preparation method of the fluorescent brightening dark-colored dyeable polypropylene fiber according to claim 5, wherein the screw rotation speed of the twin-screw extruder is 150-200 r/min, and the screw temperature is 200-220 ℃;

in the master batch, by weight, 80-120 parts of polypropylene and 40-60 parts of polyacrylic acid microspheres are added; in the spinning process, the addition amount of the master batch is 7-8 wt%; the molecular weight of the polypropylene is 146200-150700, the molecular weight distribution index is 2.5-4.5, and the melt index is 10-20 g/10 min;

the spinning process parameters are as follows: the temperature of a melt conveying pipeline is 200-260 ℃, the temperature of a melt filter is 220-260 ℃, the temperature of a spinning manifold is 220-260 ℃, the air speed of a cross air blower is 0.5-0.7 m/s, the air temperature is 15 +/-2 ℃, the temperature of a hot roller is 110 +/-10 ℃, the spinning speed is 2500-2800 m/min, and the winding angle is 7-8 degrees.

7. The method for preparing fluorescent brightening dark-colored dyeable polypropylene fiber according to claim 5, wherein the emulsifier is potassium laurate, sodium dodecyl sulfate or sodium dioctyl sulfosuccinate; the organic solvent is toluene or xylene.

8. The preparation method of the fluorescent brightening dark-colored dyeable polypropylene fiber according to claim 5, wherein in the step (1), T1 is 35-55 ℃;

in the step (3), the mass fraction of the potassium persulfate is 0.06-0.12% of the acrylate dispersion liquid; the polymerization time is 4-8 h, and the polymerization temperature is 75-95 ℃;