CN111910284A - Nylon 6 fiber with fluorescent and flame-retardant functions and preparation method thereof - Google Patents

Nylon 6 fiber with fluorescent and flame-retardant functions and preparation method thereof Download PDF

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Publication number
CN111910284A
CN111910284A CN202010656727.0A CN202010656727A CN111910284A CN 111910284 A CN111910284 A CN 111910284A CN 202010656727 A CN202010656727 A CN 202010656727A CN 111910284 A CN111910284 A CN 111910284A
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flame
retardant
fluorescent
microspheres
fiber
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CN111910284B (en
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孙正清
刘萍
孙宾
王小兵
孙小国
沈静
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Shanghai Huiyi New Material Technology Co ltd
Donghua University
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Shanghai Huiyi New Material Technology Co ltd
Donghua University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
    • C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/14—Macromolecular compounds

Abstract

The invention relates to a nylon 6 fiber with fluorescence and flame retardant functions and a preparation method thereof, the method comprises the steps of firstly adding fluorescent flame retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame retardant PA6 master batch, and then carrying out melt blending spinning by taking a mixture of the fluorescent flame retardant PA6 master batch and the PA6 as raw materials to prepare the fluorescent flame retardant PA6 fiber, wherein the polyacrylic microspheres are prepared by taking 1, 7-vinyl-perylene imide derivatives (perylene imide with vinyl group substituent at gulf site (1,7 site) and large-volume substituent at imide site) as a cross-linking agent, and the fluorescence quantum yield of the fluorescent flame retardant PA6 fiber is 80-90%; the flame retardant property is as follows: the limiting oxygen index LOI value is 30-35, and the vertical burning grade is UL 94V-0 grade. The method of the invention does not need to modify the matrix polymer structure, and has simple preparation method and low equipment requirement.

Description

Nylon 6 fiber with fluorescent and flame-retardant functions and preparation method thereof
Technical Field
The invention belongs to the technical field of nylon fibers, and relates to a nylon 6 fiber with fluorescence and flame retardant functions and a preparation method thereof.
Background
Up to now, the application of fluorescent materials to textiles has been mainly used for pigment printing or dyeing, and coating treatment methods. The disadvantages are poor durability, poor rub resistance, poor wash resistance, and limited utility. The existing fluorescent fiber is generally added into the fiber in the chemical fiber manufacturing process by using fluorescent dye and pigment. The fabric made of the fluorescent fibers is called as high-visibility warning fabric and is mainly used for high-visibility warning clothes. With the development of society, traffic accidents become one of the most common hazards in the current society, and the effective development of work for preventing and reducing traffic accidents becomes an urgent task in the current society. Statistically, 40% of traffic accidents causing death occur at night because 90% of drivers visually acquire driving information, and thus, it is a research subject to improve visibility of clothes.
For thousands of years, textiles have become necessities of life of people, the demands of the textiles are on an increasing trend along with the improvement of population and quality of life, and the inflammability of the textiles also threatens the safety of life and property of people while providing comfortable life for people. According to fire investigation, more than 20 percent of fire accidents are caused by the fact that textiles do not have the flame retardant property and are ignited and spread, so that the flame retardant finishing of the textiles is of great significance.
For some special working environments, the danger faced by workers presents a complicated and diversified trend, particularly the working environment of special operators such as fire fighting personnel, traffic police personnel, airport runway workers and the like is often dark, cold or wind and snow at night, the workers need to wear high-visibility clothes, and the high-visibility clothes are often used for high-visibility individual protective clothes. Meanwhile, workers in such an environment also need to be prevented from being injured by fire and heat, so that the required protective fabric has multiple functions of high visibility, high temperature resistance, flame retardance and the like. Polyamide fibers are one of widely used fiber types, and crystalline polyamides represented by nylon 6, nylon 66, nylon 1212, and the like have been widely used in clothing fibers and industrial materials due to their excellent properties and melt-moldability, and are widely used in the fields of automobiles, electronic and electric appliances, and the like as general engineering plastics, and polyamides having high heat resistance, high strength, good flame retardancy, and the like are required. However, the general polyamide has the defects of insufficient heat resistance, strong water absorption, low modulus, easy combustion in open fire and the like, and the existence of molten drops during combustion is very easy to cause the spread of fire, thus being very unfavorable for fire control and disaster relief. In view of this, we have conducted combined technical studies on various high-performance fibers and developed a novel high-strength nylon 6 fiber with both fluorescent and flame-retardant functions.
Patent CN108588888A relates to a method for preparing flame-retardant high-strength polyamide 6 fiber, comprising: the preparation method comprises the steps of phosphorus-containing flame-retardant chain extender preparation, modified hectorite preparation, acid or anhydride grafted modified hectorite preparation, flame-retardant high-strength PA6 composite resin preparation and flame-retardant high-strength PA6 composite fiber preparation. Specifically, the hectorite is modified by KH570 and reacts with unsaturated dibasic acid or dibasic acid anhydride to enhance the compatibility with a polymer matrix, and amino is introduced to the hectorite to enhance the acting force between the hectorite and a PA6 molecular chain, thereby improving the crystallization property of the composite resin and enhancing the mechanical property of the composite resin; the prepared flame-retardant high-strength PA6 fiber can effectively enhance the mechanical property of the fiber and improve the flame-retardant capability, and can be effectively applied to household textiles, automotive interiors, large airplane interiors, high-speed rail interiors, military operation clothes and the like. The introduction of a rigid chain segment into a PA6 main chain is realized by using a chemical modifier and physical modification synergistic effect and adopting a copolymerization and nano in-situ polymerization method, and the preparation method is complex.
Patent CN105483898A discloses a fluorescent flame-retardant multifunctional double-layer fabric, the surface layer is woven by flame-retardant yarns capable of being dyed with fluorescent color, the inner layer is woven by flame-retardant yarns which are not melted and not capable of being dyed with fluorescent color, the warp yarns of the inner layer are lifted and interwoven with the weft yarns of the surface layer to form a binding tissue, so that the two layers of fabrics are connected together. The preparation method comprises the steps of lifting warp yarns of the inner layer and interweaving weft yarns of the surface layer to form a binding structure, connecting the two layers of fabrics together, and then carrying out dyeing treatment to obtain the fluorescent flame-retardant multifunctional double-layer fabric. The flame retardant property of the flame-retardant polyester fiber needs to be improved by a textile technology, the preparation method is complex, and the equipment requirement is high.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a nylon 6 fiber with fluorescence and flame retardant functions and a preparation method thereof.
One of the purposes of the invention is to provide a nylon 6 fiber with both fluorescent and flame-retardant functions, which mainly comprises a PA6 matrix and fluorescent flame-retardant microspheres dispersed in the matrix, wherein the fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and [ (6-oxy (6H) -dibenzo- (c, e) (1,2) -oxyphosphatohexane-6-one) methyl ] -succinic acid (DDP), and the polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene imide derivatives as a cross-linking agent.
The second purpose of the invention is to provide a preparation method of the nylon 6 fiber with both fluorescence and flame retardant functions, which comprises the steps of adding the fluorescent flame retardant microspheres and the PA6 into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain fluorescent flame retardant PA6 master batches, and carrying out melt blending spinning by taking a mixture of the fluorescent flame retardant PA6 master batches and the PA6 as raw materials to obtain the fluorescent flame retardant PA6 fiber, namely the nylon 6 fiber with both fluorescence and flame retardant functions.
In order to achieve the purpose, the invention adopts the following scheme:
a nylon 6 fiber with fluorescence and flame retardant functions mainly comprises a PA6 matrix and fluorescent flame retardant microspheres dispersed in the matrix;
the fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
the polyacrylic acid microspheres are polyacrylic acid microspheres which take 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents;
the 1, 7-vinyl-perylene bisimide derivative is perylene bisimide with substituent groups with ethylene groups at gulf positions (1,7 positions) and bulky substituent groups at imide positions.
As a preferred technical scheme:
the nylon 6 fiber with the functions of fluorescence and flame retardance is characterized in that the bulky substituent is sesqui-cage siloxane or a long alkyl chain with a side chain;
the silsesquioxane is
Figure BDA0002577029500000021
R is isobutyl or isooctyl;
the long alkyl chain with side chain is
Figure BDA0002577029500000031
Wherein
Figure BDA0002577029500000032
Indicates that the linking position of the chemical bond is an N atom in an imide structure;
the substituent of the ethylene group is an alkyl chain with an ethylene group at the end group, and the alkyl chain is an alkyl chain with less than six carbons.
According to the nylon 6 fiber with the fluorescent and flame-retardant functions, in the polyacrylic acid microsphere, the molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit is 14-21.5: 125, and if the addition amount of the 1, 7-vinyl-perylene imide derivative is too small, the color of the microsphere is too light, the color is not obvious, and the too large spinnability is poor.
According to the nylon 6 fiber with the fluorescent and flame-retardant functions, the fluorescence quantum yield of the polyacrylic acid microspheres is 95-99%, and under excitation of the wavelength of 440-460 nm, a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with the wavelength of 630-645 nm is generated, and the color is orange yellow; the average diameter of the polyacrylic acid microspheres is 150-300 nm, the average pore diameter is 10-30 nm, and the porosity is 35-55%; the surface is rough and porous, the folding degree is higher, the specific surface area is large, and the reactive carboxyl groups are exposed; the phosphorus content in the fluorescent flame-retardant microspheres is 3.75-25 wt%, and the zinc content is 1.25-15 wt%.
The fluorescent flame-retardant PA6 fiber has the advantages that the breaking strength is 5.0-6.5 cN/dtex, and the elongation at break is 17-24%; the yield of the fluorescence quantum is 80-90%; the flame retardant property is as follows: the limiting oxygen index LOI value is 30-35, and the vertical burning grade is UL 94V-0 grade.
The method for testing the limiting oxygen index LOI value comprises the following steps: with reference to GB/T5454-1997, the specimen size is 150mm × 58mm, 15 blocks are provided for each warp and weft, the specimen is clamped on a specimen holder perpendicular to the combustion cylinder, the upper end of the specimen is ignited in the upward flowing oxygen-nitrogen gas flow, the combustion characteristic is observed, and the limit oxygen index value is evaluated by comparing the after-flame time or the damage length with the specified limit value. The samples were conditioned prior to testing.
The test method of the vertical burning grade comprises the following steps: with reference to GB/T5455-1997, the specimen size is 300mm x 80mm, the warp and weft of each 5 blocks are ignited by placing under a specified burner, the specimen is ignited for 12s by using a specified fire source in a specified combustion box, and the afterflame time and smoldering time of the specimen are measured after the fire source is removed. After smoldering combustion stopped, the length of the burnout was measured by a prescribed method, and the vertical burning grade was evaluated. The samples were conditioned prior to testing.
The preparation method of the nylon 6 fiber with the fluorescence and flame retardant functions comprises the steps of adding the fluorescence flame retardant microspheres and the PA6 into a double-screw extruder, carrying out melt blending and extrusion granulation to obtain fluorescence flame retardant PA6 master batches, and carrying out melt blending spinning by using a mixture of the fluorescence flame retardant PA6 master batches and the PA6 as raw materials to obtain the fluorescence flame retardant PA6 fiber, namely the nylon 6 fiber with the fluorescence and flame retardant functions;
the preparation method of the fluorescent flame-retardant microspheres comprises the following steps:
(1) mixing an emulsifier and deionized water at a temperature T1 to form a system I;
(2) firstly, dissolving methyl acrylate and 1, 7-vinyl-perylene bisimide derivatives in an organic solvent, adding the mixture into a system I, and mixing at a temperature of T2 to obtain a system II;
(3) firstly, stirring a system II for a certain time, and then adding potassium persulfate into the system II to initiate polymerization to obtain a polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature (23 +/-2 ℃), filtering, washing and drying to obtain polyacrylate microspheres;
(4) mixing polyacrylate microspheres with sodium hydroxide ethanol solution, heating, refluxing, cooling, filtering, and drying (washing with water for several times, washing with dilute hydrochloric acid for one time, and washing with water for several times before drying) to obtain polyacrylic microspheres (solid powder);
(5) dispersing polyacrylic acid microspheres in an organic solvent to prepare a suspension;
(6) adding zinc acetate dihydrate and DDP ([ (6-oxo-6H-dibenzo [ c, e ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid) into the suspension, dissolving uniformly under the stirring condition (stirring is mechanical stirring or magnetic stirring, the stirring speed is 200-500 rpm, the stirring time is 0.5-1H, ultrasonic oscillation is carried out simultaneously, the power is 600-1200W) at room temperature (23 +/-2 ℃), dripping deionized water at a certain speed, and separating out a white precipitate to obtain a mixed solution;
(7) and filtering, washing (washing with a large amount of deionized water, and replacing the water in the mixture with absolute ethyl alcohol) and drying the mixture to obtain the fluorescent flame-retardant microspheres.
According to the preparation method of the nylon 6 fiber with the fluorescent and flame-retardant functions, the mass ratio of the fluorescent flame-retardant microspheres in the fluorescent flame-retardant PA6 master batch to PA6 is 1: 2.5-9; during melt blending spinning, the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 11.5-13.3.
The preparation method of the nylon 6 fiber with the fluorescent and flame-retardant functions comprises the following steps: the spinning temperature is 250-270 ℃ (250-255 ℃ in the first zone, 266-270 ℃ in the second zone, 265-270 ℃ in the third zone and 270 ℃ in the fourth zone), the spinning speed is 800-1200 m/min, the drafting multiple is 3-4 times, and the drafting speed is 450-500 m/min; the drafting temperature is 50-70 ℃, and the heat setting temperature is 100-120 ℃; the viscosity of the PA6 is 2-2.8 dl/g; the heating temperature of the double-screw extruder is 230-255 ℃, and the rotating speed of the screws is 300-380 r/min; the temperature of each heating section of the extruder is as follows: a first section is 230 ℃; the second section is 240 ℃; the third section is 255 ℃; the fourth section is 250 ℃; the five stages are 245 ℃.
According to the preparation method of the nylon 6 fiber with the fluorescence and flame retardant functions, the emulsifier is potassium laurate, sodium dodecyl sulfate or sodium dioctyl sulfosuccinate; the organic solvent is toluene or xylene.
The preparation method of the nylon 6 fiber with the fluorescent and flame-retardant functions comprises the following steps of (1), wherein T1 is 35-55 ℃, and the mixing time is 3-8 min;
in the system II in the step (2), the content of the emulsifier is 0.4-0.7 wt%, the content of the methyl acrylate is 4-6 wt%, the stirring speed is 300-500 r/min, and the stirring time is 15-35 min; the content of the 1, 7-vinyl-perylene bisimide derivative is 9-15 wt%, and the content of the organic solvent is 6-10 wt%; t2 is 75-95 ℃;
in the step (3), the addition amount of the potassium persulfate is 1-5 wt% of the polyacrylate dispersion liquid; the polymerization time is 4-8 h, and the polymerization temperature is 75-95 ℃; the drying temperature is 90-140 ℃;
the concentration of the sodium hydroxide ethanol solution in the step (4) is 1-2 mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1-3; the heating reflux time is 9-11 h, and the drying temperature is 90-110 ℃;
in the step (5), the organic solvent is DMF, chloroform or acetone, and the mass fraction of the polyacrylic acid microspheres in the suspension is 5-20%;
in the step (6), the adding amount of zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, and the mass ratio of the polyacrylic acid microspheres to the DDP is 1: 1-1.5; the certain speed is 0.5-1 drop/s;
in the step (7), drying is carried out under vacuum condition, wherein the vacuum degree is-0.1 MPa, the drying time is 8-12 h, and the drying temperature is 40 ℃.
The principle of the invention is as follows:
the 1, 7-vinyl-perylene imide derivative has fluorescence property, and the 1, 7-vinyl-perylene imide derivative with a bulky imide site substituent group can ensure that the 1, 7-vinyl-perylene imide derivative has great steric hindrance when being aggregated through pi-pi interaction, and can more easily exist in a system in a monomolecular state under the condition of a solvent. Finally, the 1, 7-vinyl-perylene imide derivative can be used as a cross-linking agent to enter the polyacrylate microsphere in a monomolecular state. The 1, 7-vinyl-perylene imide derivative is also a fluorescent molecule, and the 1, 7-vinyl-perylene imide derivative generates fluorescence quenching when being aggregated through pi-pi interaction, so that the fluorescence quantum yield is reduced, and the related fluorescence performance is reduced. According to the invention, the 1, 7-vinyl-perylene bisimide derivative enters a system in a monomolecular state, so that the aggregation of the derivative is effectively avoided, the occurrence of fluorescence quenching is avoided, and the good fluorescence property of the 1, 7-vinyl-perylene bisimide derivative is maintained; DDP belongs to an organic phosphorus heterocyclic compound containing two hydroxyl groups, is a halogen-free reaction type flame retardant, is mainly applied to flame retardant treatment of high polymer materials such as PET, PBT, PTT, nylon, epoxy resin, polyurethane, unsaturated polyester resin and the like, and ensures that the product has excellent flame retardant effect. The solubility in hydrocarbon and ketone solvents is very low, and the solvent is easily dissolved in organic solvents such as DMF, DMSO and the like. High melting point, good thermal stability and non-volatility. The synthetic flame-retardant slice can be used for drawing films and spinning filaments, has strong dyeability, and has no migration and attenuation of flame-retardant performance after being washed by water or dry-cleaned for many times. Has the characteristics of long-time flame retardant property, low smoke density, good anti-dripping effect, no toxicity of smoke and the like.
The invention adopts 1, 7-vinyl-perylene imide derivatives as cross-linking agents to prepare polyacrylate microspheres, and hydrolyzes the polyacrylate microspheres into polyacrylic microspheres, so that the polyacrylic microspheres have porous structures, large specific surface areas and multiple reactive carboxyl groups are exposed. Then, loading DDP on polyacrylic acid microspheres to prepare fluorescent flame-retardant microspheres; the loading mechanism of DDP is: zn2+The compound can generate chelation with carboxyl in DDP molecules and carboxyl on polyacrylic microspheres, and the DDP molecules are chemically fixed in the microspheres; at the same time, Zn2+Also can generate chelation with a plurality of DDP molecules to ensure that the DDP molecules are not dissolved outIn a microsphere; p ═ O and C ═ O and Zn in DDP2+The coordination of (a) will also enhance the interaction; the DDP, the polyacrylic acid and the zinc acetate dihydrate in the fluorescent flame-retardant microsphere are fixed together under the action, and the carboxyl groups in the polyacrylic acid microsphere are far away from the 1, 7-vinyl-perylene bisimide derivative, so that the carboxylic acid groups in the microsphere participate in chelation and cannot generate great influence on the fluorescence performance; so that the microspheres have flame retardant effect.
The invention further blends and granulates the fluorescent flame-retardant microspheres and polyamide 6, and uses a melt spinning method to spin nylon 6 fiber with both fluorescent and flame-retardant functions; the flame retardant has high flame retardant performance under the condition of small addition amount (relatively small phosphorus content is used, the higher phosphorus content in the fiber is caused by DDP loaded by the microspheres, and the synergistic effect of the metal zinc and the phosphorus flame retardant is realized); the action force of the carboxyl functionalized polyacrylic acid microspheres and the polyamide is enhanced by utilizing the hydrogen bond action of the exposed carboxyl and the amide group in the polyamide structure, so that the carboxyl functionalized polyacrylic acid microspheres have good dispersion performance in the polyamide matrix, and the influence on various performances (breaking strength, breaking elongation and linear density) of the fiber is small.
Has the advantages that:
(1) the nylon 6 fiber with the fluorescent and flame-retardant functions can meet the production requirements of fabrics with the fluorescent and flame-retardant properties in life and production, and can ensure that the fabric has better flame-retardant property under the condition of lower phosphorus content;
(2) according to the preparation method of the nylon 6 fiber with the fluorescence and flame retardant functions, the nylon 6 fiber with the fluorescence and flame retardant functions is prepared mainly by adding the functional microspheres, the modification of a matrix polymer structure is not needed, the preparation method is simple, and the equipment requirement is low.
Detailed Description
The 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
Figure BDA0002577029500000061
(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
Figure BDA0002577029500000062
(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
Figure BDA0002577029500000063
(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 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
Figure BDA0002577029500000071
(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
Figure BDA0002577029500000072
(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.
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
Figure BDA0002577029500000073
(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 3
The preparation method of the 1, 7-vinyl-perylene bisimide derivative comprises the following steps:
the imide site bulky substituent access method comprises the following steps:
the crude product PTCDA-Br was charged in a 250mL three-necked flask
Figure BDA0002577029500000081
(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
Figure BDA0002577029500000082
(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
Figure BDA0002577029500000083
(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 4
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
Figure BDA0002577029500000084
(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,
Figure BDA0002577029500000091
(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
Figure BDA0002577029500000092
(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 5
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
Figure BDA0002577029500000093
(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
Figure BDA0002577029500000094
(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. Followed by the bodyAnhydrous potassium carbonate (55.4mg,0.40mmol), 18-crown-6-ether (105.73mg,0.40mmol) were added to the mixture and pipetted
Figure BDA0002577029500000101
(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 6
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
Figure BDA0002577029500000102
(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
Figure BDA0002577029500000103
(4.5mmol), R is isooctyl, glacial acetic acid (16mL,140 mmol). Heating to 85 ℃ under the protection of nitrogen, and continuing the reaction for 7 hours. After the reaction was completed, it was cooled to room temperature, and then 120.00mL of methanol was added thereto, followed by stirring overnight. 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
Figure BDA0002577029500000104
(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 7
A preparation method of nylon 6 fiber with fluorescence and flame retardant functions comprises the following steps:
(1) preparing fluorescent flame-retardant microspheres:
(1.1) mixing potassium laurate and deionized water at a temperature 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%, the content of 1, 7-vinyl-perylene imide derivatives is 13.6 wt%, the content of toluene is 10 wt%, and the content of potassium laurate is 0.4 wt%;
(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 1 wt% of the polyacrylate dispersion liquid; the polymerization time is 4h, and the polymerization temperature is 75 ℃;
(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 1mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1; the heating reflux time is 9h, and the drying temperature is 90 ℃;
the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 14: 125; the average diameter of the polyacrylic acid microspheres is 150nm, the average pore diameter is 10nm, and the porosity is 35%; the fluorescence quantum yield of the polyacrylic acid microspheres is 95%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;
(1.5) dispersing polyacrylic acid microspheres in DMF to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 5%;
(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.2 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1, and the adding amount of the deionized water is 1 time of the volume of the polyacrylic acid microspheres;
(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 8h, and the drying temperature is 40 ℃;
the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
(2) preparing fluorescent flame-retardant PA6 master batch:
adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PA6 in the fluorescent flame-retardant PA6 master batch is 1:2.5, the heating temperature of a double-screw extruder is 230 ℃, and the screw rotating speed is 300 r/min;
(3) preparing the nylon 6 fiber with the fluorescent and flame-retardant functions:
the fluorescent flame-retardant PA6 fiber, namely the nylon 6 fiber with both fluorescent and flame-retardant functions, is prepared by taking a mixture of fluorescent flame-retardant PA6 master batches and PA6 with the viscosity of 2dl/g as raw materials and carrying out melt blending spinning; wherein the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 11.5;
the melt blending spinning process comprises the following steps: the spinning temperature is 250 ℃, the spinning speed is 800m/min, the drafting multiple is 50 times, and the drafting speed is 450 m/min; the drawing temperature is 50 ℃ and the heat setting temperature is 100 ℃.
The finally prepared nylon 6 fiber with the functions of fluorescence and flame retardance has the breaking strength of 6.5cN/dtex and the elongation at break of 17 percent; the fluorescence quantum yield is 80%; the flame retardant property is as follows: the limiting oxygen index LOI value is 30, and the vertical burning grade is UL 94V-0 grade.
Example 8
A preparation method of nylon 6 fiber with fluorescence and flame retardant functions comprises the following steps:
(1) preparing fluorescent flame-retardant microspheres:
(1.1) mixing potassium laurate and deionized water at a temperature 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 addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 5h, and the polymerization temperature is 76 ℃;
(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 3; the heating reflux time is 11h, and the drying temperature is 98 ℃;
the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 16: 125; the average diameter of the polyacrylic acid microspheres is 207nm, the average pore diameter is 27nm, and the porosity is 50%; the fluorescence quantum yield of the polyacrylic acid microspheres is 98%, and characteristic fluorescence emission peaks of 630-645 nm 1, 7-vinyl-perylene imide derivatives are generated under excitation of a wavelength of 440-460 nm;
(1.5) dispersing polyacrylic acid microspheres in DMF to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 7%;
(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.1 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.2, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;
(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 9h, and the drying temperature is 40 ℃;
the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
(2) preparing fluorescent flame-retardant PA6 master batch:
adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch; wherein the mass ratio of the fluorescent flame-retardant microspheres in the fluorescent flame-retardant PA6 master batch to PA6 is 1:3, the heating temperature of a double-screw extruder is 230 ℃, and the screw rotating speed is 308 r/min;
(3) preparing the nylon 6 fiber with the fluorescent and flame-retardant functions:
the fluorescent flame-retardant PA6 fiber, namely the nylon 6 fiber with both fluorescent and flame-retardant functions, is prepared by taking a mixture of fluorescent flame-retardant PA6 master batches and PA6 with the viscosity of 2dl/g as raw materials and carrying out melt blending spinning; wherein the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 11.7;
the melt blending spinning process comprises the following steps: the spinning temperature is 269 ℃, the spinning speed is 1045m/min, the drafting multiple is 56 times, and the drafting speed is 472 m/min; the drawing temperature was 56 ℃ and the heat-setting temperature was 120 ℃.
The finally prepared nylon 6 fiber with the functions of fluorescence and flame retardance has the breaking strength of 6.2cN/dtex and the elongation at break of 18 percent; the fluorescence quantum yield is 88%; the flame retardant property is as follows: the limiting oxygen index LOI value is 31, and the vertical burning grade is UL 94V-0 grade.
Example 9
A preparation method of nylon 6 fiber with fluorescence and flame retardant functions comprises the following steps:
(1) preparing fluorescent flame-retardant microspheres:
(1.1) mixing potassium laurate and deionized water at a temperature of T1(40 ℃) 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(80 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 4 wt%, the content of 1, 7-vinyl-perylene imide derivatives is 12.5 wt%, the content of toluene is 9 wt%, and the content of potassium laurate is 0.5 wt%;
(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 1 wt% of the polyacrylate dispersion liquid; the polymerization time is 4h, and the polymerization temperature is 80 ℃;
(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 3; the heating reflux time is 10h, and the drying temperature is 96 ℃;
the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 20: 125; the average diameter of the polyacrylic acid microspheres is 235nm, the average pore diameter is 19nm, and the porosity is 53%; the fluorescence quantum yield of the polyacrylic acid microspheres is 99%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;
(1.5) dispersing polyacrylic acid microspheres in chloroform to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 17%;
(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.5 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.5, and the adding amount of the deionized water is 1.1 times of the volume of the polyacrylic acid microspheres;
(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 10h, and the drying temperature is 40 ℃;
the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
(2) preparing fluorescent flame-retardant PA6 master batch:
adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch; wherein the mass ratio of the fluorescent flame-retardant microspheres in the fluorescent flame-retardant PA6 master batch to the PA6 is 1:5, the heating temperature of a double-screw extruder is 246 ℃, and the rotating speed of a screw is 300 r/min;
(3) preparing the nylon 6 fiber with the fluorescent and flame-retardant functions:
the fluorescent flame-retardant PA6 fiber, namely the nylon 6 fiber with both fluorescent and flame-retardant functions, is prepared by taking a mixture of fluorescent flame-retardant PA6 master batches and PA6 with the viscosity of 2.2dl/g as raw materials and carrying out melt blending spinning; wherein the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 12;
the melt blending spinning process comprises the following steps: the spinning temperature is 253 ℃, the spinning speed is 1011m/min, the drafting multiple is 53 times, and the drafting speed is 467 m/min; the drawing temperature was 53 ℃ and the heat-setting temperature was 115 ℃.
The finally prepared nylon 6 fiber with the functions of fluorescence and flame retardance has the breaking strength of 6.0cN/dtex and the elongation at break of 23 percent; the fluorescence quantum yield is 85%; the flame retardant property is as follows: the limiting oxygen index LOI value is 30, and the vertical burning grade is UL 94V-0 grade.
Example 10
A preparation method of nylon 6 fiber with fluorescence and flame retardant functions comprises the following steps:
(1) preparing fluorescent flame-retardant microspheres:
(1.1) mixing sodium lauryl sulfate and deionized water at a temperature T1(39 ℃) to form system I;
(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene bisimide derivative (prepared in example 6) in toluene, adding the mixture into the system I, and mixing at the temperature of T2(93 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 5 wt%, the content of 1, 7-vinyl-perylene imide derivative is 14.5 wt%, the content of toluene is 10 wt%, and the content of sodium dodecyl sulfate is 0.5 wt%;
(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 5h, and the polymerization temperature is 88 ℃;
(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1; the heating reflux time is 10h, and the drying temperature is 100 ℃;
the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 21.5: 125; the average diameter of the polyacrylic acid microspheres is 201nm, the average pore diameter is 21nm, and the porosity is 48%; the fluorescence quantum yield of the polyacrylic acid microspheres is 98%, and characteristic fluorescence emission peaks of 630-645 nm 1, 7-vinyl-perylene imide derivatives are generated under excitation of a wavelength of 440-460 nm;
(1.5) dispersing polyacrylic acid microspheres in acetone to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 5%;
(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.5 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.3, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;
(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 8h, and the drying temperature is 40 ℃;
the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
(2) preparing fluorescent flame-retardant PA6 master batch:
adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch; wherein the mass ratio of the fluorescent flame-retardant microspheres in the fluorescent flame-retardant PA6 master batch to the PA6 is 1:5, the heating temperature of a double-screw extruder is 230 ℃, and the screw rotating speed is 369 r/min;
(3) preparing the nylon 6 fiber with the fluorescent and flame-retardant functions:
the fluorescent flame-retardant PA6 fiber, namely the nylon 6 fiber with both fluorescent and flame-retardant functions, is prepared by taking a mixture of fluorescent flame-retardant PA6 master batches and PA6 with the viscosity of 2.5dl/g as raw materials and carrying out melt blending spinning; wherein the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 12.8;
the melt blending spinning process comprises the following steps: the spinning temperature is 261 ℃, the spinning speed is 970m/min, the drafting multiple is 63 times, and the drafting speed is 459 m/min; the drawing temperature was 63 ℃ and the heat-setting temperature was 110 ℃.
The finally prepared nylon 6 fiber with the functions of fluorescence and flame retardance has the breaking strength of 6.5cN/dtex and the elongation at break of 17 percent; the fluorescence quantum yield is 87%; the flame retardant property is as follows: the limiting oxygen index LOI value is 30, and the vertical burning grade is UL 94V-0 grade.
Example 11
A preparation method of nylon 6 fiber with fluorescence and flame retardant functions comprises the following steps:
(1) preparing fluorescent flame-retardant microspheres:
(1.1) mixing sodium lauryl sulfate and deionized water at a temperature T1(55 ℃) to form system I;
(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene bisimide derivative (prepared in example 3) in toluene, adding the mixture into the system I, and mixing at the temperature of T2(93 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 6 wt%, the content of 1, 7-vinyl-perylene imide derivatives is 10.4 wt%, the content of toluene is 8 wt%, and the content of sodium dodecyl sulfate is 0.6 wt%;
(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 8h, and the polymerization temperature is 94 ℃;
(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1; the heating reflux time is 10h, and the drying temperature is 101 ℃;
the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 14.5: 125; the average diameter of the polyacrylic acid microspheres is 290nm, the average pore diameter is 17nm, and the porosity is 55%; the fluorescence quantum yield of the polyacrylic acid microspheres is 98%, and characteristic fluorescence emission peaks of 630-645 nm 1, 7-vinyl-perylene imide derivatives are generated under excitation of a wavelength of 440-460 nm;
(1.5) dispersing polyacrylic acid microspheres in chloroform to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 7%;
(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 1 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.2, and the adding amount of the deionized water is 1.1 times of the volume of the polyacrylic acid microspheres;
(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 11h, and the drying temperature is 40 ℃;
the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
(2) preparing fluorescent flame-retardant PA6 master batch:
adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch; wherein the mass ratio of the fluorescent flame-retardant microspheres in the fluorescent flame-retardant PA6 master batch to the PA6 is 1:6, the heating temperature of a double-screw extruder is 230 ℃, and the screw rotating speed is 356 r/min;
(3) preparing the nylon 6 fiber with the fluorescent and flame-retardant functions:
the fluorescent flame-retardant PA6 fiber, namely the nylon 6 fiber with both fluorescent and flame-retardant functions, is prepared by taking a mixture of fluorescent flame-retardant PA6 master batches and PA6 with the viscosity of 2.8dl/g as raw materials and carrying out melt blending spinning; wherein the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 13.3;
the melt blending spinning process comprises the following steps: the spinning temperature is 250 ℃, the spinning speed is 1072m/min, the drafting multiple is 61 times, and the drafting speed is 466 m/min; the drawing temperature was 61 ℃ and the heat-setting temperature was 115 ℃.
The finally prepared nylon 6 fiber with the functions of fluorescence and flame retardance has the breaking strength of 6.2cN/dtex and the elongation at break of 21 percent; the fluorescence quantum yield is 90%; the flame retardant property is as follows: the limiting oxygen index LOI value is 35, and the vertical burning grade is UL 94V-0 grade.
Example 12
A preparation method of nylon 6 fiber with fluorescence and flame retardant functions comprises the following steps:
(1) preparing fluorescent flame-retardant microspheres:
(1.1) mixing dioctyl sodium sulfosuccinate and deionized water at a temperature T1(38 ℃) to form a system I;
(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene 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 addition amount of the potassium persulfate is 1 wt% of the polyacrylate dispersion liquid; the polymerization time is 7h, and the polymerization temperature is 84 ℃;
(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 1mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1; the heating reflux time is 11h, and the drying temperature is 99 ℃;
the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 14.3: 125; the average diameter of the polyacrylic acid microspheres is 288nm, the average pore diameter is 25nm, and the porosity is 47%; the fluorescence quantum yield of the polyacrylic acid microspheres is 97%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;
(1.5) dispersing polyacrylic acid microspheres in acetone to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 18%;
(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 1 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;
(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 10h, and the drying temperature is 40 ℃;
the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
(2) preparing fluorescent flame-retardant PA6 master batch:
adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch; wherein the mass ratio of the fluorescent flame-retardant microspheres in the fluorescent flame-retardant PA6 master batch to the PA6 is 1:8, the heating temperature of a double-screw extruder is 234 ℃, and the screw rotating speed is 349 r/min;
(3) preparing the nylon 6 fiber with the fluorescent and flame-retardant functions:
the fluorescent flame-retardant PA6 fiber, namely the nylon 6 fiber with both fluorescent and flame-retardant functions, is prepared by taking a mixture of fluorescent flame-retardant PA6 master batches and PA6 with the viscosity of 2.5dl/g as raw materials and carrying out melt blending spinning; wherein the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 12.5;
the melt blending spinning process comprises the following steps: the spinning temperature is 253 ℃, the spinning speed is 812m/min, the drafting multiple is 57 times, and the drafting speed is 476 m/min; the drawing temperature was 57 ℃ and the heat-setting temperature was 100 ℃.
The finally prepared nylon 6 fiber with the functions of fluorescence and flame retardance has the breaking strength of 6.4cN/dtex and the elongation at break of 17 percent; the fluorescence quantum yield is 84%; the flame retardant property is as follows: the limiting oxygen index LOI value is 33, and the vertical burning grade is UL 94V-0 grade.
Example 13
A preparation method of nylon 6 fiber with fluorescence and flame retardant functions comprises the following steps:
(1) preparing fluorescent flame-retardant microspheres:
(1.1) mixing dioctyl sodium sulfosuccinate and deionized water at a temperature T1(36 ℃) to form a system I;
(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene imide derivative (prepared in example 5) in xylene, adding the mixture into the system I, and mixing at the temperature of T2(92 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 5 wt%, the content of 1, 7-vinyl-perylene imide derivative is 15 wt%, the content of xylene is 6 wt%, and the content of dioctyl sodium sulfosuccinate is 0.7 wt%;
(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 5h, and the polymerization temperature is 92 ℃;
(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 1mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 3; the heating reflux time is 11h, and the drying temperature is 101 ℃;
the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 15: 125; the average diameter of the polyacrylic acid microspheres is 290nm, the average pore diameter is 19nm, and the porosity is 50%; the fluorescence quantum yield of the polyacrylic acid microspheres is 99%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;
(1.5) dispersing polyacrylic acid microspheres in DMF to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 17%;
(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.5 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.2, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;
(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 8h, and the drying temperature is 40 ℃;
the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
(2) preparing fluorescent flame-retardant PA6 master batch:
adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch; wherein the mass ratio of the fluorescent flame-retardant microspheres in the fluorescent flame-retardant PA6 master batch to the PA6 is 1:9, the heating temperature of a double-screw extruder is 253 ℃, and the rotating speed of a screw is 341 r/min;
(3) preparing the nylon 6 fiber with the fluorescent and flame-retardant functions:
the fluorescent flame-retardant PA6 fiber, namely the nylon 6 fiber with both fluorescent and flame-retardant functions, is prepared by taking a mixture of fluorescent flame-retardant PA6 master batches and PA6 with the viscosity of 2.5dl/g as raw materials and carrying out melt blending spinning; wherein the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 13;
the melt blending spinning process comprises the following steps: the spinning temperature is 259 ℃, the spinning speed is 1077m/min, the drafting multiple is 70 times, and the drafting speed is 482 m/min; the drawing temperature was 70 ℃ and the heat-setting temperature was 100 ℃.
The finally prepared nylon 6 fiber with the functions of fluorescence and flame retardance has the breaking strength of 5.8cN/dtex and the elongation at break of 19 percent; the fluorescence quantum yield is 80%; the flame retardant property is as follows: the limiting oxygen index LOI value is 34, and the vertical burning grade is UL 94V-0 grade.
Example 14
A preparation method of nylon 6 fiber with fluorescence and flame retardant functions comprises the following steps:
(1) preparing fluorescent flame-retardant microspheres:
(1.1) mixing dioctyl sodium sulfosuccinate and deionized water at a temperature T1(55 ℃) to form a system I;
(1.2) dissolving methyl acrylate and the 1, 7-vinyl-perylene imide derivative (prepared in example 6) in xylene, adding the mixture into the system I, and mixing at the temperature of T2(95 ℃) to obtain a system II; in the system II, the content of methyl acrylate is 6 wt%, the content of 1, 7-vinyl-perylene imide derivatives is 9 wt%, the content of xylene is 9.3 wt%, and the content of dioctyl sodium sulfosuccinate is 0.7 wt%;
(1.3) firstly, adding potassium persulfate into the system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres; wherein the addition amount of the potassium persulfate is 2 wt% of the polyacrylate dispersion liquid; the polymerization time is 8h, and the polymerization temperature is 95 ℃;
(1.4) mixing the polyacrylate microspheres with a sodium hydroxide ethanol solution with the concentration of 2mol/L, heating and refluxing, cooling, filtering and drying to obtain the polyacrylic microspheres; wherein the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 3; heating and refluxing for 11h, and drying at 110 deg.C;
the prepared polyacrylic acid microspheres are polyacrylic acid microspheres using 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents, wherein the molar ratio of the 1, 7-vinyl-perylene bisimide derivatives to acrylic acid structural units in the polyacrylic acid microspheres is 21: 125; the average diameter of the polyacrylic acid microspheres is 300nm, the average pore diameter is 30nm, and the porosity is 55%; the fluorescence quantum yield of the polyacrylic acid microspheres is 99%, and the characteristic fluorescence emission peak of the 630-645 nm 1, 7-vinyl-perylene imide derivative is generated under the excitation of the wavelength of 440-460 nm;
(1.5) dispersing polyacrylic acid microspheres in chloroform to prepare a suspension; the mass fraction of the polyacrylic acid microspheres in the suspension is 20%;
(1.6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dropwise adding deionized water at the rate of 0.5 drop/s to obtain a mixed solution; wherein the adding amount of the zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, the mass ratio of the polyacrylic acid microspheres to the DDP is 1:1.2, and the adding amount of the deionized water is 1.2 times of the volume of the polyacrylic acid microspheres;
(1.7) filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres; wherein, the drying is carried out under the vacuum condition, the vacuum degree is-0.1 MPa, the drying time is 12h, and the drying temperature is 40 ℃;
the prepared fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
(2) preparing fluorescent flame-retardant PA6 master batch:
adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder for melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch; wherein the mass ratio of the fluorescent flame-retardant microspheres to the PA6 in the fluorescent flame-retardant PA6 master batch is 1:8.5, the heating temperature of a double-screw extruder is 255 ℃, and the screw rotating speed is 380 r/min;
(3) preparing the nylon 6 fiber with the fluorescent and flame-retardant functions:
the fluorescent flame-retardant PA6 fiber, namely the nylon 6 fiber with both fluorescent and flame-retardant functions, is prepared by taking a mixture of fluorescent flame-retardant PA6 master batches and PA6 with the viscosity of 2dl/g as raw materials and carrying out melt blending spinning; wherein the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 13.3;
the melt blending spinning process comprises the following steps: the spinning temperature is 270 ℃, the spinning speed is 1200m/min, the drafting multiple is 70 times, and the drafting speed is 500 m/min; the drawing temperature was 70 ℃ and the heat-setting temperature was 120 ℃.
The finally prepared nylon 6 fiber with the functions of fluorescence and flame retardance has the breaking strength of 5.0cN/dtex and the elongation at break of 24 percent; the fluorescence quantum yield is 90%; the flame retardant property is as follows: the limiting oxygen index LOI value is 35, and the vertical burning grade is UL 94V-0 grade.

Claims (10)

1. A nylon 6 fiber with fluorescence and flame retardant functions is characterized in that: mainly comprises a PA6 matrix and fluorescent flame-retardant microspheres dispersed in the matrix;
the fluorescent flame-retardant microspheres are polyacrylic acid microspheres loaded with zinc acetate dihydrate and DDP;
the polyacrylic acid microspheres are polyacrylic acid microspheres which take 1, 7-vinyl-perylene bisimide derivatives as cross-linking agents;
the 1, 7-vinyl-perylene bisimide derivative is perylene bisimide with substituent groups with ethylene groups at gulf positions (1,7 positions) and bulky substituent groups at imide positions.
2. The fluorescent and flame-retardant nylon 6 fiber according to claim 1, wherein the bulky substituent is a silsesquioxane or a long alkyl chain with a side chain;
the silsesquioxane is
Figure FDA0002577029490000011
R is isobutyl or isooctyl;
the long alkyl chain with side chain is
Figure FDA0002577029490000012
Wherein
Figure FDA0002577029490000013
Indicates that the linking position of the chemical bond is an N atom in an imide structure;
the substituent of the ethylene group is an alkyl chain with an ethylene group at the end group, and the alkyl chain is an alkyl chain with less than six carbons.
3. The nylon 6 fiber with both fluorescent and flame-retardant functions of claim 1, wherein in the polyacrylic acid microsphere, the molar ratio of the 1, 7-vinyl-perylene imide derivative to the acrylic acid structural unit is 14-21.5: 125.
4. The nylon 6 fiber with both fluorescence and flame retardant functions of claim 1, wherein the yield of fluorescence quantum of the polyacrylic acid microsphere is 95-99%, and a characteristic fluorescence emission peak of the 1, 7-vinyl-perylene imide derivative with a wavelength of 630-645 nm is generated under excitation with a wavelength of 440-460 nm; the average diameter of the polyacrylic acid microspheres is 150-300 nm, the average pore diameter is 10-30 nm, and the porosity is 35-55%; the phosphorus content in the fluorescent flame-retardant microspheres is 3.75-25 wt%, and the zinc content is 1.25-15 wt%.
5. The fluorescent and flame-retardant nylon 6 fiber according to claim 1, wherein the fluorescent and flame-retardant PA6 fiber has a breaking strength of 5.0-6.5 cN/dtex and an elongation at break of 17-24%; the yield of the fluorescence quantum is 80-90%; the flame retardant property is as follows: the limiting oxygen index LOI value is 30-35, and the vertical burning grade is UL 94V-0 grade.
6. The method for preparing nylon 6 fiber with both fluorescent and flame retardant functions as claimed in any one of claims 1 to 5, which is characterized in that: adding the fluorescent flame-retardant microspheres and PA6 into a double-screw extruder, carrying out melt blending and extrusion granulation to prepare fluorescent flame-retardant PA6 master batch, and carrying out melt blending spinning by taking a mixture of the fluorescent flame-retardant PA6 master batch and PA6 as a raw material to prepare a fluorescent flame-retardant PA6 fiber, namely a nylon 6 fiber with both fluorescent and flame-retardant functions;
the preparation method of the fluorescent flame-retardant microspheres comprises the following steps:
(1) mixing an emulsifier and deionized water at a temperature T1 to form a system I;
(2) firstly, dissolving methyl acrylate and 1, 7-vinyl-perylene bisimide derivatives in an organic solvent, adding the mixture into a system I, and mixing at a temperature of T2 to obtain a system II;
(3) firstly, adding potassium persulfate into a system II to initiate polymerization to obtain polyacrylate dispersion liquid; cooling the polyacrylate dispersion liquid to room temperature, filtering, washing and drying to obtain polyacrylate microspheres;
(4) mixing polyacrylate microspheres with a sodium hydroxide ethanol solution, heating and refluxing, cooling, filtering and drying to obtain polyacrylic microspheres;
(5) dispersing polyacrylic acid microspheres in an organic solvent to prepare a suspension;
(6) adding zinc acetate dihydrate and DDP into the suspension, dissolving uniformly at room temperature, and dripping deionized water at a certain speed to obtain a mixed solution;
(7) and filtering, washing and drying the mixed solution to obtain the fluorescent flame-retardant microspheres.
7. The preparation method of the nylon 6 fiber with the fluorescent and flame-retardant functions according to claim 6, wherein the mass ratio of the fluorescent flame-retardant microspheres in the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 2.5-9; during melt blending spinning, the mass ratio of the fluorescent flame-retardant PA6 master batch to the PA6 is 1: 11.5-13.3.
8. The preparation method of the nylon 6 fiber with the fluorescent and flame-retardant functions as claimed in claim 6, wherein the melt blending spinning process comprises the following steps: the spinning temperature is 250-270 ℃, the spinning speed is 800-1200 m/min, the drafting multiple is 3-4 times, and the drafting speed is 450-500 m/min; the drafting temperature is 50-70 ℃, and the heat setting temperature is 100-120 ℃; the viscosity of the PA6 is 2-2.8 dl/g; the heating temperature of the double-screw extruder is 230-255 ℃, and the rotating speed of the screws is 300-380 r/min.
9. The method for preparing nylon 6 fiber with fluorescence and flame retardant functions according to claim 6, wherein the emulsifier is potassium laurate, sodium dodecyl sulfate or sodium dioctyl sulfosuccinate; the organic solvent is toluene or xylene.
10. The preparation method of the nylon 6 fiber with the fluorescent and flame-retardant functions as claimed in claim 6, wherein in the step (1), T1 is 35-55 ℃;
in the system II in the step (2), the content of the emulsifier is 0.4-0.7 wt%, the content of the methyl acrylate is 4-6 wt%, the content of the 1, 7-vinyl-perylene imide derivative is 9-15 wt%, and the content of the organic solvent is 6-10 wt%; t2 is 75-95 ℃;
in the step (3), the addition amount of the potassium persulfate is 1-5 wt% of the polyacrylate dispersion liquid; the polymerization time is 4-8 h, and the polymerization temperature is 75-95 ℃;
the concentration of the sodium hydroxide ethanol solution in the step (4) is 1-2 mol/L, and the volume ratio of the polyacrylate microspheres to the sodium hydroxide ethanol solution is 1: 1-3; the heating reflux time is 9-11 h, and the drying temperature is 90-110 ℃;
in the step (5), the organic solvent is DMF, chloroform or acetone, and the mass fraction of the polyacrylic acid microspheres in the suspension is 5-20%;
in the step (6), the adding amount of zinc acetate dihydrate is the same as the mass of the polyacrylic acid microspheres, and the mass ratio of the polyacrylic acid microspheres to the DDP is 1: 1-1.5; the certain speed is 0.5-1 drop/s;
in the step (7), drying is carried out under vacuum condition, wherein the vacuum degree is-0.1 MPa, the drying time is 8-12 h, and the drying temperature is 40 ℃.
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