CN120758991A

CN120758991A - A kind of anti-ultraviolet high flame retardant polyester fiber and preparation method thereof

Info

Publication number: CN120758991A
Application number: CN202510896265.2A
Authority: CN
Inventors: 柳敦雷; 陆佳颖; 韦开顺; 柴森光; 王永锋; 姬洪; 张义成; 周文龙
Original assignee: Jiangsu Hengke Advanced Materials Co Ltd
Current assignee: Jiangsu Hengke Advanced Materials Co Ltd
Priority date: 2025-06-30
Filing date: 2025-06-30
Publication date: 2025-10-10
Also published as: CN121065846A

Abstract

The present invention discloses an anti-ultraviolet highly flame-retardant polyester fiber and a preparation method thereof. The raw materials for preparing the polyester fiber include the following components by weight: 100 parts of polyester chips, 20-60 parts of core-shell flame-retardant anti-ultraviolet particles, and 2-4.5 parts of anti-dripping agents. The present invention uses a porous alumina-titanium dioxide composite as a carrier, and combines a magnesium hydroxide flame retardant, iron-doped carbon dots with photothermal properties, and auxiliary agents (antioxidants and ultraviolet absorbers) with it to construct a structural system to form a plurality of active component loads: functionalized flame-retardant particles, which are then coated with a polyurethane microporous membrane to obtain a core-shell flame-retardant anti-ultraviolet particle. Adding it to the polyester fiber can significantly improve the anti-ultraviolet performance and flame retardant performance of the polyester fiber. The polyester fiber provided by the present invention can adaptively increase the release rate of the ultraviolet absorber and antioxidant when the ultraviolet property in the environment is enhanced, thereby providing more optimized protection for the polyester fiber matrix at this time.

Description

Ultraviolet-resistant high-flame-retardance polyester fiber and preparation method thereof

Technical Field

The invention relates to the field of polyester fiber materials, in particular to an ultraviolet-resistant high-flame-retardance polyester fiber and a preparation method thereof.

Background

Polyester fiber commonly called as polyester is a synthetic fiber prepared from organic dibasic acid and dihydric alcohol through chemical polycondensation, and has the advantages of high breaking strength and elastic modulus, moderate rebound resilience, excellent heat setting effect, good wear resistance, stable chemical performance, good heat resistance and light resistance, better corrosion resistance and stability to weak acid and weak base. It has wide application in the manufacture of household textiles, industrial textiles, and the like.

When the polyester fiber is applied to outdoor environments, such as tarpaulins, vehicle roofs, ropes, packaging materials (such as cement, non-woven fabrics for sand and stone packaging bags and the like), nonwoven polyester fiber cloths for buildings, and other nonwoven fabrics for industries, the outdoor environments often have a great deal of ultraviolet irradiation and attack of some oxidizing substances, so that the ultraviolet resistance and the oxidation resistance of the polyester fiber are challenged. The ultraviolet absorber and/or inorganic filler with ultraviolet resistance and the antioxidant are/is added, so that the ultraviolet resistance and the antioxidant performance of the polyester fiber can be improved, and in the traditional scheme, the ultraviolet absorber and the antioxidant are usually directly added into a polyester system, for example, a thermal insulation and moisture-conducting multifunctional polyester fiber disclosed in patent CN111979585A and a preparation method thereof, a flexible packaging belt of the polyester fiber disclosed in patent CN105802146A and a preparation method thereof, an antibacterial elastic polyester fiber disclosed in patent CN120041963A and a preparation method thereof, a extinction PET fiber slice spinning preparation process disclosed in patent CN119956520A and the like. The main problems are that the ageing of the anti-ultraviolet and anti-aging agent is short when the adding amount is small, the anti-ultraviolet and anti-aging agent is easy to aggregate due to the compatibility problem to influence the performance of the polyester when the adding amount is large, and the anti-ultraviolet and anti-aging agent is directly exposed in a polyester system in a large amount, so that the anti-ultraviolet and anti-aging agent can be accelerated to lose efficacy due to decomposition, surface migration and the like, and the ageing of the anti-ultraviolet and anti-aging agent is shortened. The construction of the slow release system can realize the long-acting release of the active ingredients and prolong the efficacy of the active ingredients, such as a slow release yellowing-resistant auxiliary agent disclosed in patent CN120158132A and the application thereof in paint, a slow release antioxidant disclosed in patent CN120098689A and the preparation method and application thereof, and the like. However, in such a scheme, the release rate of the active ingredient is not controllable, for example, the release rate of the ultraviolet absorber is not affected no matter whether the ultraviolet light in the environment is strong or weak, and only depends on the slow release system itself. If the release rate and the release amount of the ultraviolet absorbent are adaptively increased when the ultraviolet light in the environment is strong, a better and more intelligent ultraviolet light resistant function can be provided for the matrix at the moment, and obviously, the solutions cannot achieve the aim.

Therefore, there is a need in the art for improvements that provide a more reliable solution.

Disclosure of Invention

The invention aims to solve the technical problem of providing an ultraviolet-resistant high-flame-retardance polyester fiber and a preparation method thereof aiming at the defects in the prior art.

In order to solve the technical problems, the invention adopts the technical scheme that the first aspect of the invention provides an anti-ultraviolet high-flame-retardance polyester fiber, which comprises the following raw materials in parts by weight:

s1, preparing a porous carrier, wherein the porous carrier is a compound of porous alumina and titanium dioxide;

S2, loading magnesium hydroxide on the porous carrier to obtain flame-retardant particles;

s3, modifying a photo-thermal agent on the flame-retardant particles to obtain functionalized flame-retardant particles, wherein the photo-thermal agent is carbon dots with photo-thermal properties;

S4, loading an auxiliary agent on the functionalized flame-retardant particles to obtain core particles, wherein the auxiliary agent comprises an antioxidant and an ultraviolet absorber;

S5, coating the polyurethane microporous membrane on the core particles to obtain the core-shell type flame-retardant ultraviolet-resistant particles.

Preferably, the anti-dripping agent is at least one of melamine, benzoguanamine and triallyl isocyanurate, the antioxidant is at least one of antioxidant 1010, antioxidant 618, antioxidant 1076 and antioxidant 1098, and the ultraviolet absorbent is at least one of UV-P, UV-1, UV-9, UVBP-4, UV-234 and UVP-327.

Preferably, the core-shell flame-retardant ultraviolet-resistant particles are prepared by the following method:

S1, preparing a porous carrier, namely preparing a compound of porous alumina and titanium dioxide, namely the porous carrier by taking tetrabutyl titanate as a titanium source, AI (NO ₃)₃·9H₂ O as an aluminum source, cetyl trimethyl ammonium bromide as a template agent and ammonium bicarbonate as a precipitator through hydrothermal reaction and roasting;

S2, carrying out blending reaction on the porous carrier, mgCl ₂ and NaOH, and loading magnesium hydroxide on the porous carrier to obtain flame-retardant particles;

S3, loading magnesium hydroxide, namely taking glucose, ferric citrate, 2',7' -dichlorofluorescein diacetate, 4-dimethylaminopyridine and indocyanine green as raw materials, taking a mixed solution of ethanol and water as a solvent, and synthesizing carbon points with photo-thermal properties on the flame-retardant particles in situ by a hydrothermal method to obtain functionalized flame-retardant particles, wherein the carbon points are photo-thermal agents;

s4, loading an auxiliary agent, namely loading the auxiliary agent on the functional flame-retardant particles by adopting a method of supergravity auxiliary impregnation to obtain core particles, wherein the auxiliary agent comprises an antioxidant and an ultraviolet absorber;

s5, coating the polyurethane microporous membrane, namely coating the polyurethane microporous membrane on the core particles to obtain the core-shell flame-retardant ultraviolet-resistant particles.

Preferably, step S1 specifically comprises:

Adding tetrabutyl titanate into n-butanol to obtain solution A, adding AI (NO ₃)₃·9H₂ O and hexadecyl trimethyl ammonium bromide into deionized water, adding ammonium bicarbonate, stirring, adding solution A, adding the obtained mixture into a reaction kettle, reacting at 150-170deg.C for 6-24 hr, and calcining the solid product at 400-550deg.C for 2-8 hr to obtain porous carrier.

Preferably, the step S2 is specifically that a porous carrier is taken and dispersed in deionized water, mgCl ₂ is added, naOH aqueous solution is dripped, and after dripping is completed, stirring reaction is carried out for 1-4 hours at 40-60 ℃, filtering, washing and drying are carried out, thus obtaining the flame-retardant particles.

Preferably, the step S3 specifically includes:

S3-1, dispersing flame-retardant particles and ferric citrate in deionized water at 60-80 ℃ to obtain a mixed solution 1, adding glucose, 2',7' -dichlorofluorescein diacetate, 4-dimethylaminopyridine and indocyanine green into a mixed solvent consisting of ethanol and deionized water, and stirring to obtain a mixed solution 2;

s3-2, adding the mixed solution 2 into the mixed solution 1, transferring the obtained precursor solution into a reaction kettle, reacting for 4-16 hours at 165-190 ℃, and carrying out suction filtration, washing and drying to obtain the functional flame-retardant particles.

Preferably, step S4 specifically includes:

s4-1, adding an antioxidant and an ultraviolet absorbent into acetone to prepare an auxiliary agent impregnating solution with the antioxidant concentration of 5-20g/L and the ultraviolet absorbent concentration of 3-12 g/L;

s4-2, adding the functionalized flame-retardant particles into the impregnating solution, performing ultrasonic dispersion for 0.5-2h, then placing the particles in a supergravity packed bed, performing treatment under the supergravity condition of 25-100 times of gravity acceleration for 2-8h, then taking down the particles, standing the particles for 1-4h, and performing filtration, washing and drying to obtain the core particles.

Preferably, step S5 specifically includes:

S5-1, adding PPG, TDI and hydroxypropyl silicone oil into acetone, heating to 55-75 ℃, dropwise adding triethylene diamine, stirring and reacting for 1-3h, adding butanediol and ethylenediamine, stirring and reacting for 1.5-6h at 70-75 ℃, and distilling under reduced pressure to remove acetone to obtain modified polyurethane emulsion;

S5-2, adding modified polyurethane emulsion, inner core particles and polyethylene glycol into a mixed solution composed of butanone and DMF, stirring and reacting for 15-60min at 65-75 ℃, standing for 5-30min, centrifugally separating, adding the obtained solid product into DMF, stirring, suction filtering, adding the solid product into deionized water at 70-80 ℃, stirring for 2-8h, suction filtering, and drying for h to obtain the core-shell flame-retardant ultraviolet-resistant particles.

s1, preparing a porous carrier:

Adding 0.85-3.4mL of tetrabutyl titanate into 25-100mL of n-butanol, stirring for 2-10min to obtain solution A, adding 5-20g of AI (NO ₃)₃·9H₂ O, 0.12-0.5g of cetyltrimethylammonium bromide into 75-300mL of deionized water, stirring for 5-20min, adding 4-16g of ammonium bicarbonate, stirring for 15-60min, adding solution A, performing ultrasonic dispersion for 0.5-2h, adding the obtained mixture into a reaction kettle, reacting for 6-24h at 150-170 ℃, cooling to room temperature, performing suction filtration, washing, drying, roasting for 2-8h at 650-750 ℃, and grinding to obtain a porous carrier;

S2, loading magnesium hydroxide on a porous carrier:

dispersing 2.5-10g of porous carrier in 100-400mL of deionized water, adding 1.5-6.3g of MgCl ₂, dropwise adding 30-150mL of 1mol/L NaOH aqueous solution under stirring, stirring at 40-60 ℃ for reaction for 1-4h, filtering, washing and drying to obtain flame-retardant particles;

s3, modifying a photo-thermal agent on the flame-retardant particles:

S3-1, dispersing 2.5-10g of flame-retardant particles and 612-2450mg of ferric citrate in 50-200mL of deionized water with the temperature of 60-80 ℃ to obtain a mixed solution 1, adding 450-1800mg of glucose, 200-814mg of 2',7' -dichlorofluorescein diacetate, 122-488mg of 4-dimethylaminopyridine and 220-930mg of indocyanine green into a mixed solvent consisting of 20-80mL of ethanol and 30-120mL of deionized water, and stirring for 5-30min to obtain a mixed solution 2;

S3-2, adding the mixed solution 2 into the mixed solution 1 under stirring, performing ultrasonic dispersion for 5-20min at 60-80 ℃, transferring the obtained precursor solution into a reaction kettle, reacting for 4-16h at 165-190 ℃, cooling, performing suction filtration, washing and drying to obtain functionalized flame-retardant particles;

s4, loading an auxiliary agent on the functionalized flame-retardant particles:

S4-1, adding an antioxidant and an ultraviolet absorbent into acetone, and uniformly stirring to prepare an auxiliary agent impregnating solution with the concentration of the antioxidant of 5-20g/L and the concentration of the ultraviolet absorbent of 3-12 g/L;

s4-2, adding 2.5-10g of functionalized flame-retardant particles into 50-200mL of impregnating solution, performing ultrasonic dispersion for 0.5-2h, then placing the solution in a hypergravity packed bed, taking the solution out after 2-8h of treatment under the hypergravity condition of 100-400 times of gravity acceleration, standing for 1-4h, filtering, washing and drying to obtain core particles;

S5, coating a polyurethane microporous membrane on the kernel particles:

S5-1, adding 2.5-10g PPG, 1.75-7g TDI and 0.7-2.8g hydroxypropyl silicone oil into 50-200mL acetone, heating to 55-75 ℃ under the protection of nitrogen, then dropwise adding 0.005-0.03g triethylene diamine, stirring and reacting for 1-3h, adding 1-4mL butanediol and 0.4-1.6mL ethylenediamine, stirring and reacting for 1.5-6h at 70-75 ℃, cooling to room temperature, and distilling under reduced pressure to remove acetone to obtain modified polyurethane emulsion;

s5-2, adding 2.5-10g of modified polyurethane emulsion, 1.25-5g of kernel particles and 0.28-1.12g of polyethylene glycol into a mixed solution consisting of 15-60mL of butanone and 15-60mL of DMF, stirring for 5-30min, stirring and reacting for 15-60min at 65-75 ℃, standing for 5-30min, cooling to room temperature, centrifuging, adding the obtained solid product into 25-100mL of DMF, stirring for 5-20min, carrying out suction filtration, adding the solid product into 50-200mL of deionized water with the temperature of 70-80 ℃, stirring for 2-8h, carrying out suction filtration, and drying to obtain the core-shell flame-retardant ultraviolet-resistant particles.

s1, preparing a porous carrier:

adding 1.7mL of tetrabutyl titanate into 50mL of n-butanol, stirring for 5min to obtain solution A, adding 10g of AI (NO ₃)₃·9H₂ O, 0.25g of hexadecyltrimethyl ammonium bromide into 150mL of deionized water, stirring for 10min, adding 7.9g of ammonium bicarbonate, stirring for 30min, adding the solution A, performing ultrasonic dispersion for 1h, adding the obtained mixture into a reaction kettle, reacting for 12h at 160 ℃, cooling to room temperature, performing suction filtration, washing and drying, roasting at 700 ℃ for 4h, and grinding to obtain a porous carrier;

S2, loading magnesium hydroxide on a porous carrier:

Adding 5g of porous carrier into 200mL of deionized water, performing ultrasonic dispersion for 30min, then adding 3.15g of MgCl ₂, stirring for 15min, dropwise adding 75mL of 1mol/L NaOH aqueous solution under stirring, stirring at 50 ℃ for reaction for 2h after the dropwise adding is completed, filtering, washing and drying to obtain flame-retardant particles;

s3, modifying a photo-thermal agent on the flame-retardant particles:

S3-1, adding 5g of flame-retardant particles and 1225mg of ferric citrate into 100mL of deionized water with the temperature of 70 ℃ and performing ultrasonic dispersion for 30min to obtain a mixed solution 1, adding 900mg of glucose, 407mg of 2',7' -dichloro-dihydro-fluorescein diacetate, 244mg of 4-dimethylaminopyridine and 465mg of indocyanine green into a mixed solvent consisting of 40mL of ethanol and 60mL of deionized water, and stirring for 15min to obtain a mixed solution 2;

S3-2, adding the mixed solution 2 into the mixed solution 1 under stirring, performing ultrasonic dispersion for 10min at 70 ℃ to obtain a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined reaction kettle, reacting for 8h at 175 ℃, cooling, performing suction filtration, washing and drying to obtain functionalized flame-retardant particles;

s4, loading an auxiliary agent on the functionalized flame-retardant particles:

S4-1, adding an antioxidant and an ultraviolet absorbent into acetone, and uniformly stirring to prepare an auxiliary agent impregnating solution with the concentration of the antioxidant of 10g/L and the concentration of the ultraviolet absorbent of 6 g/L;

s4-2, adding 5g of functionalized flame-retardant particles into 100mL of impregnating solution, performing ultrasonic dispersion for 1h, then placing the mixture in a supergravity packed bed, treating the mixture for 4h under the supergravity condition of 150 times of gravity acceleration, taking the mixture out of the supergravity packed bed, standing the mixture for 2h, filtering, washing and drying the mixture to obtain core particles;

S5, coating a polyurethane microporous membrane on the kernel particles:

S5-1, adding 5g PPG, 3.5g TDI and 1.4g hydroxypropyl silicone oil into 100mL acetone, heating to 65 ℃ under the protection of nitrogen, then dropwise adding 0.015g triethylene diamine, stirring and reacting for 1.5h, adding 2mL butanediol and 0.8mL ethylenediamine, stirring and reacting for 3h at 72 ℃, cooling to room temperature, and distilling under reduced pressure to remove acetone to obtain modified polyurethane emulsion;

S5-2, adding 5g of modified polyurethane emulsion, 2.5g of core particles and 0.56g of polyethylene glycol into a mixed solution consisting of 30mL of butanone and 30mL of DMF, stirring for 15min, stirring for reaction at 70 ℃ for 30min, standing for 15min, cooling to room temperature, centrifugally separating, adding the obtained solid product into 50mL of DMF, stirring for 10min, carrying out suction filtration, adding the solid product into 100mL of deionized water at 75 ℃, stirring for 4h, carrying out suction filtration, and carrying out vacuum drying on the solid product at 50 ℃ for 12h to obtain the core-shell flame retardant anti-ultraviolet particles.

The invention also provides a preparation method of the ultraviolet-resistant high-flame-retardance polyester fiber, which comprises the following steps:

1) Vacuum drying the polyester chip at 100-120 ℃ for 6-24 hours, and then stirring and mixing the polyester chip with core-shell flame-retardant anti-ultraviolet particles and anti-dripping agents to obtain a polyester mixed material;

2) And (3) melting and extruding the polyester mixed material at 230-245 ℃, and spinning the obtained melt to obtain the ultraviolet-resistant high-flame-retardance polyester fiber, wherein the spinning temperature is 250-270 ℃, and the spinning speed is 600-900m/min.

The mechanism of the invention is as follows:

1. preparation mechanism

(1) Firstly, AI (NO ₃)₃·9H₂ O is used as an aluminum source, cetyl trimethyl ammonium bromide is used as a template agent, ammonium bicarbonate is used as a precipitator, and alumina with a porous structure is prepared by a traditional hydrothermal reaction and roasting method, and the method is characterized in that tetrabutyl titanate is used as a titanium source, titanium dioxide is doped in the alumina with the porous structure, and a porous alumina-titanium dioxide compound, namely a porous carrier, is obtained and is marked as TiO ₂-Al₂O₃.

On the one hand, tiO ₂-Al₂O₃ is used as a carrier to realize the loading of various active components (magnesium hydroxide, carbon dots and auxiliary agents) and can provide the slow release function of the auxiliary agents by virtue of the porous structure. On the other hand, the addition of alumina to the polyester fiber can enhance the wear resistance, strength and thermal stability thereof, which contributes to improving the flame retarding ability of the polyester fiber, while the doped titanium dioxide has excellent ultraviolet light absorbing ability and can improve the strength, weather resistance and heat resistance of the fiber.

(2) And then, by means of developed pore structure and large specific surface area of the porous carrier, magnesium hydroxide is loaded on the porous carrier as a flame retardant to obtain flame-retardant particles, which are marked as TiO ₂-Al₂O₃@Mg(OH)₂. The magnesium hydroxide is used as a common inorganic flame retardant, and releases water molecules and absorbs a large amount of heat when being heated and decomposed, so that the temperature of the polyester fiber is reduced, the combustion process is delayed or prevented, and the flame retardant property of the polyester fiber can be obviously improved.

(3) And then glucose, 2',7' -dichlorofluorescein diacetate, 4-dimethylaminopyridine and indocyanine green are used as composite carbon sources, ferric citrate is used as a doping component, and iron-doped carbon points with photo-thermal performance are synthesized on the flame-retardant particles in situ by a one-pot hydrothermal method, wherein the carbon points are photo-thermal agents, and the functionalized flame-retardant particles are obtained and are marked as Ti ₂-Al₂O₃@Mg(OH)₂ @Fe-CDs. In the preparation process, on one hand, components such as a composite carbon source are adsorbed on the surface of TiO ₂-Al₂O₃@Mg(OH)₂ or enter the pores of the TiO ₂-Al₂O₃@Mg(OH)₂ through the adsorption action of the rich pore structure of TiO ₂-Al₂O₃@Mg(OH)₂, on the other hand, ferric citrate is firstly mixed with TiO ₂-Al₂O₃@Mg(OH)₂, ferric ions are combined with hydroxyl groups on the surface of TiO ₂-Al₂O₃@Mg(OH)₂ through the coordination and other actions, and then the ferric ions can be combined with the components in the composite carbon source through the coordination and other actions of carboxyl groups, amino groups and other functional groups, so that the components can be adsorbed by TiO ₂-Al₂O₃@Mg(OH)₂ in a large amount, and favorable conditions are created for in-situ deposition preparation of carbon dots on the TiO ₂-Al₂O₃@Mg(OH)₂.

The in-situ modified synthesized iron-doped carbon dot has excellent ultraviolet absorption performance, can obviously improve the ultraviolet resistance of the polyester fiber, simultaneously has good photo-thermal performance (performance of converting light energy into heat energy), can realize local heating effect while absorbing ultraviolet rays, can be used as a photo-thermal agent with excellent performance, and can play a role in carrying out self-adaptive intelligent regulation on micropores of a polyurethane microporous membrane along with the condition of the ultraviolet content in the core-shell type flame-retardant ultraviolet-resistant particle structure system.

2',7' -Dichloro-dihydro-fluorescein diacetate (DCFH-DA) is used as a carbon source to prepare a carbon dot with photo-thermal performance, and Lv Ju and the like are reported to prepare a Cu doped carbon dot with photo-thermal performance through hydrothermal reaction by adopting the DCFH-DA and Cu < 2+ >, so that the red photo-thermal performance is verified, the Cu doped carbon dot can be used as a photo-thermal agent in photo-thermal treatment (preparation, characterization and performance [ J ]. Fine chemical engineering, 2024, 41 (8): 1745-1753.), but the photo-thermal efficiency is only 21.7% (808 and nm laser irradiation) after test, and the photo-thermal efficiency is necessary to be further improved. In order to prepare the carbon dot with ultraviolet light thermal performance, the invention carries out series improvement on the basis of the carbon dot, glucose, 4-dimethylaminopyridine and indocyanine green are added as composite carbon sources, fe ³⁺ with variable valence is adopted to replace Cu ²⁺ for doping, and finally the prepared carbon dot shows excellent ultraviolet light absorption capacity and ultraviolet light thermal performance, and the photo-thermal efficiency can reach 45.2%.

The doping of Fe ³⁺ can change the electron cloud distribution of carbon points, increase the electron cloud density, form new impurity energy levels, reduce the band gap width of the material, expand the light absorption range, and expose more active sites in the carbon point skeleton by iron anchoring, thereby enhancing the capturing efficiency of incident photons, and finally improving the light absorption efficiency and the energy utilization rate, and enhancing the ultraviolet absorption performance and the photo-thermal efficiency. The addition of 4-dimethylaminopyridine enriches the strong electron donating groups in the carbon sites and improves the light absorption coefficient and photo-thermal properties, which is consistent with the report in literature "Dongmei Xi,Ming Xiao,Jianfang Cao,Luyang Zhao,Ning Xu,Saran Long,Jiangli Fan,Kun Shao,Wen Sun*,Xuehai Yan,and Xiaojun Peng*.NIR Light-Driving Barrier-Free Group Rotation in Nanoparticles with an 88.3% Photothermal Conversion Efﬁciency for Photothermal Therapy.Adv.Mater.2020,32,190785". Indocyanine green (ICG) is a near infrared fluorescent dye with high absorptivity.

(4) The method comprises the steps of preparing a polyester fiber matrix, carrying out super-gravity assisted impregnation, namely loading an antioxidant and an ultraviolet absorbent on the functionalized flame-retardant particles by utilizing a pore structure with abundant functionalized flame-retardant particles, and obtaining core particles, wherein the super-gravity assisted impregnation is adopted, so that the impregnation loading efficiency and loading capacity can be improved, the antioxidant and the ultraviolet absorbent are loaded in the pores, and a better slow release effect can be realized, so that the antioxidant and the ultraviolet absorbent in the polyester fiber matrix can be released slowly for a long time, a longer lasting effect is provided, the premature failure of the antioxidant and the ultraviolet absorbent in a polyester system caused by the aggregation, the indication migration and other sites can be effectively avoided, and the adverse effect on the polyester fiber matrix is relieved.

(5) And finally coating polyurethane microporous membranes on the core particles to obtain core-shell flame-retardant ultraviolet-resistant particles, adding hydroxypropyl silicone oil into PPG and TDI serving as conventional polyurethane preparation raw materials, preparing modified polyurethane emulsion by using triethylene diamine as a catalyst, and blending the core particles and the modified polyurethane emulsion by using a conventional solvent-non-solvent method (Wang Quanjie, zhang Yuzhou, yang n, and the like), wherein the influence of different pore-forming agents on the permeability of the polyurethane microporous membranes [ J ] leather science and engineering, 2011 (3): 6.DOI: 10.3969/j.issn.1004-7964.2011.03.005.), using polyethylene glycol as a pore-forming agent, using DMF as a solvent and using water as a non-solvent, and coating the polyurethane microporous membranes on the core particles.

One of the disadvantages of the application of the inorganic reinforcing particles TiO ₂、Al₂O₃、Mg(OH)₂ in the polyester fiber system is poor system compatibility and difficult uniform dispersion, and in addition, the TiO ₂ as an anti-ultraviolet active component and the Mg (OH) ₂ as a flame retardant active component also have the problems of easy premature failure of component activity, deteriorated substrate performance and the like caused by aggregation, surface migration and the like in the polyester system. The coating of the polyurethane microporous membrane can obviously improve the compatibility of the core particles and the polyester fiber system, and can simultaneously solve the problem that inorganic components TiO ₂、Al₂O₃、Mg(OH)₂ and Fe-CDs are difficult to uniformly disperse in the polyester fiber system by matching with a multi-component organic combination structure on the core particles. In addition, the polyurethane microporous membrane is coated to avoid direct contact between TiO ₂、Mg(OH)₂ and polyester, so that the negative influence on the performance of a polyester system can be reduced, the phenomena of aggregation, surface migration and the like in the polyester system are slowed down, and the polyurethane microporous membrane has a certain shielding effect on TiO ₂, can avoid premature consumption of ultraviolet absorption activity, has a certain slow release performance, and can prolong the action effect. When a fire occurs, the polyurethane microporous membrane rapidly expands and melts at a high temperature to fully expose Mg (OH) ₂, so that the timely exertion of the flame retardant effect of the polyurethane microporous membrane is not affected.

In the second aspect, the polyurethane also has good elasticity and wear resistance, and the addition of the polyester fiber can improve the elasticity and comfort of the polyester fiber and enhance the durability of the fabric. The addition of the hydroxypropyl silicone oil can improve the water repellency (Chen Zufen, lin Weihong) and improve the waterproof capability of the polyester fiber by synthesizing and applying the comb-type waterborne polyurethane coated organic silicon fluorine-free high-efficiency water repellent [ J ]. Guangzhou chemical industry, 2023, 51 (11): 71-74 ].

In the third aspect, unlike the conventional polymer coating modification mode, the polyurethane film with a pore structure is coated on the core particles, and the matching of the film structure and the iron-doped carbon dots with photo-thermal properties inside can realize 'self-adaptive regulation' of the anti-ultraviolet performance and the oxidation resistance, and the regulation results are that the stronger the ultraviolet rays are, the larger the amount of the antioxidant and the ultraviolet absorbent released by the core-shell flame-retardant anti-ultraviolet particles is, the more the carbon dots with the anti-ultraviolet performance and the porous carrier are exposed, so that the self-adaptive enhancement of the provided anti-ultraviolet performance and oxidation resistance is realized, and the following further explanation is given:

when the polyester fiber is irradiated by ultraviolet rays, the photo-thermal agent (Fe-CDs) absorbs ultraviolet rays to play a role in resisting ultraviolet rays, meanwhile, the local temperature is increased, the effect of thermal expansion and contraction is achieved, the micropores of the polyurethane microporous membrane are expanded, the permeability of the membrane is enhanced, the molecular motion is accelerated by the increase of the temperature, the release of an antioxidant and the ultraviolet ray absorber loaded in a porous carrier can be promoted, the two effects are combined, more antioxidant and ultraviolet ray absorber are released into the polyester fiber system from the core-shell type flame-retardant ultraviolet-resistant particles, the increase of the ultraviolet ray absorber can improve the ultraviolet absorption performance to match the enhancement of the ultraviolet rays at the moment, meanwhile, the exposure of TiO ₂ and Fe-CDs in the core particles is increased due to the increase of the permeability of TiO ₂, the ultraviolet absorption capability provided by TiO ₂ is enhanced, but strong oxidizing substances bad to the polyester system structure are easily generated due to the increase of the release amount of the antioxidant, and the negative effects of the strong oxidizing substances on the ultraviolet rays can be prevented from being captured in time when the ultraviolet rays are absorbed by the TiO ₂. The Fe-CDs are exposed and increased to absorb more ultraviolet rays and generate more heat, so that micropores of the polyurethane microporous membrane are further expanded, a gain effect of ultraviolet resistance is generated, the intelligent self-adaptive regulation and control of ultraviolet resistance and oxidation resistance is finally realized, the regulation and control effect can enable active components in the system to adaptively regulate the protective performance provided by the active components according to environmental changes, the efficacy of the active components can be prolonged, and the effect of the active components can be fully exerted.

It should be understood that the upper limit of the temperature of the local heating caused by the core-shell flame-retardant anti-ultraviolet particles in the invention is far from the level causing combustion, and after the core-shell flame-retardant anti-ultraviolet particles are added into the polyester fiber, the upper limit of the temperature does not exceed 100 ℃ in a normal outdoor application scene (when the addition of the core-shell flame-retardant anti-ultraviolet particles is maximum in a photo-thermal performance experiment, the upper limit of the local maximum temperature in the polyester fiber is about 97 ℃) mainly because of the limitation of light source power (the ultraviolet light source mainly comes from illumination in a normal outdoor application scene, the intensity of the ultraviolet light source has a normal range), the balance of heat generation and heat dissipation, the photo-thermal efficiency of the functional flame-retardant particles and the like, so that hidden dangers such as fire caused by the temperature rise cannot be caused. However, it should be noted that, due to the existence of the photo-thermal property, the polyester fiber prepared in the invention is not suitable for being applied to textile products worn next to the skin to avoid scalding the human body, but is very suitable for being applied to many non-wearable products in an outdoor application environment, and a great amount of ultraviolet irradiation and invasion of some oxidizing substances are inevitably existed in the outdoor environment, so that great challenges are presented to the ultraviolet resistance and the oxidation resistance of the polyester fiber. The polyester fiber of the invention has the ultraviolet resistance and oxidation resistance which are self-adaptively regulated, and can prolong the ultraviolet resistance and oxidation resistance, so the polyester fiber is very suitable for such scenes as tarpaulins, vehicle roofs, ropes, packaging materials (such as cement, non-woven fabrics for sand and stone packaging bags and the like), non-woven polyester fiber cloth for buildings and other non-woven fabrics for industries and the like.

The beneficial effects of the invention are as follows:

The invention takes a porous alumina-titanium dioxide compound as a carrier, combines a magnesium hydroxide flame retardant, an iron-doped carbon point with photo-thermal performance, an auxiliary agent (an antioxidant and an ultraviolet absorber) and the magnesium hydroxide flame retardant to form a structural system loaded by various active components, namely, functional flame-retardant particles, and then coating polyurethane microporous films to obtain a core-shell flame-retardant ultraviolet-resistant particle, which is added into polyester fibers to obviously improve the ultraviolet resistance and flame retardance of the polyester fibers;

According to the invention, the polyurethane film with a pore structure is coated on the inner core particles loaded with active components such as an antioxidant, an ultraviolet absorber and the like, and the polyurethane film is matched with iron-doped carbon dots with photo-thermal properties in the inner core particles, so that the self-adaptive regulation and control of the anti-ultraviolet performance and the anti-oxidation performance can be realized, and the regulation and control result is that the stronger the ultraviolet rays are, the larger the amount of the antioxidant and the ultraviolet absorber released in the core-shell flame-retardant anti-ultraviolet particles are, the more the carbon dots with the anti-ultraviolet performance and the porous carrier are exposed, so that the self-adaptive enhancement of the anti-ultraviolet performance and the anti-oxidation performance is realized, and the performances of the active components such as the antioxidant and the ultraviolet absorber can be better exerted, the effects are prolonged, and the anti-ultraviolet effect and the aging effect of the polyester fiber are improved. The self-adaptive regulation and control enables the polyester fiber prepared by the invention to have excellent application effect and great application potential in non-wearing fabric products related to outdoor application environments, such as tarpaulins, vehicle roofs, ropes, packaging materials (such as cement, non-woven fabrics for sand and stone packaging bags and the like), non-woven polyester fiber cloth for buildings and other non-woven fabrics for industries.

Drawings

FIG. 1 is an infrared absorption spectrum of the porous support (TiO ₂-Al₂O₃) and the functionalized flame retardant particles [ TiO ₂-Al₂O₃@Mg(OH)₂ @Fe-CDs ] prepared in example 1;

FIG. 2 is a temperature-time plot of the flame retardant particles [ TiO ₂-Al₂O₃@Mg(OH)₂ ] and functionalized flame retardant particles [ TiO ₂-Al₂O₃@Mg(OH)₂ @Fe-CDs ] prepared in example 1;

FIG. 3 is a photo-thermal conversion efficiency test result of the core-shell type flame retardant and ultraviolet resistant particles in examples 1 to 4 and comparative examples 2 to 3;

FIG. 4 is an ultraviolet visible absorption spectrum of the core-shell type flame retardant ultraviolet resistant particles prepared in example 1, comparative example 1 and comparative example 4;

FIG. 5 is a graph showing the results of the ultraviolet absorbent release performance test of the core-shell type flame retardant ultraviolet resistant particles prepared in example 1;

FIG. 6 is a graph showing the ultraviolet resistance (UVA) test results of the polyester fibers prepared in examples 1 to 4 and comparative examples 1 to 6;

FIG. 7 is a graph showing the ultraviolet resistance (UVB) test results of the polyester fibers prepared in examples 1 to 4 and comparative examples 1 to 6;

FIG. 8 is a graph showing the results of flame retardant property tests of the polyester fibers prepared in examples 1 to 4 and comparative examples 1 to 6;

FIG. 9 is a graph showing the results of breaking strength test of the polyester fibers prepared in examples 1 to 4 and comparative examples 1 to 6;

FIG. 10 is a graph showing the results of the test for retention of breaking strength after aging of the polyester fibers prepared in examples 1 to 4 and comparative examples 1 to 6.

Detailed Description

The present invention is described in further detail below with reference to examples to enable those skilled in the art to practice the same by referring to the description.

It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.

The test methods used in the following examples are conventional methods unless otherwise specified. The material reagents and the like used in the following examples are commercially available unless otherwise specified. The following examples were conducted under conventional conditions or conditions recommended by the manufacturer, without specifying the specific conditions. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.

The main raw material sources in the following examples and comparative examples are explained as follows:

polyester chip, model CB-602, relative viscosity 0.8dl/g, acid value 35mg KOH/g, shanghai Co., ltd;

Triallyl isocyanurate with an average particle size of 4 μm and manufactured by Jiangsu Minlin chemical engineering Co., ltd;

Tetrabutyl titanate, cetyl trimethylammonium bromide, jiangsu Minlin chemical engineering Co., ltd;

2',7' -dichlorofluorescein diacetate (DCFH-DA), CAS number 4091-99-0, shanghai Source leaf Biotechnology Co., ltd;

4-dimethylaminopyridine, nanjing chemical Co., ltd;

Indocyanine green, brand, caramar, shanghai purple-reagent factory;

antioxidant 1010, ultraviolet absorber UV-9, nanjing Milan chemical Co., ltd;

hydroxypropyl silicone oil, double-end hydroxypropyl silicone oil, 2000 molecular weight, hydroxyl content 1.7%, darling chemical Co., ltd., hubei province;

PPG (Polypropylene glycol), polypropylene glycol 2000, shanghai Hongzhi chemical engineering Co., ltd;

polyethylene glycol, PEG-1000, a petrochemical plant in sea and in Jiangsu province;

Toluene Diisocyanate (TDI), triethylenediamine (Triethylenediamine), nantong Runfeng petrochemical Co., ltd;

magnesium hydroxide with an average particle size of 5 μm, nantong Runfeng petrochemical Co., ltd;

example 1

The ultraviolet-resistant high-flame-retardance polyester fiber comprises the following raw materials in parts by weight: 100 parts of polyester chips, 42 parts of core-shell flame-retardant ultraviolet-resistant particles and 3 parts of anti-drip agent; the anti-dripping agent is triallyl isocyanurate;

the preparation method of the polyester fiber comprises the following steps:

1) Vacuum drying the polyester chip for 12 hours at 110 ℃, and then stirring and mixing the polyester chip with the core-shell flame-retardant anti-ultraviolet particles and anti-dripping agent for 30 minutes at 500rpm to obtain a polyester mixed material;

2) Adding the polyester mixed material into a double-screw extruder, and carrying out melt extrusion at 240 ℃ to obtain melt, spinning the melt to obtain the ultraviolet-resistant high-flame-retardance polyester fiber, wherein the spinning temperature is 265 ℃, the spinning speed is 750m/min, the drawing multiple is 2 times, and the drawing rate is 700 m/mm.

The core-shell type flame-retardant ultraviolet-resistant particle is prepared by the following steps:

s1, preparing a porous carrier:

Adding 1.7mL of tetrabutyl titanate into 50mL of n-butanol, stirring for 5min to obtain solution A, adding 10g of AI (NO ₃)₃·9H₂ O, 0.25g of hexadecyltrimethyl ammonium bromide into 150mL of deionized water, stirring for 10min, adding 7.9g of ammonium bicarbonate, stirring for 30min, adding the solution A, performing ultrasonic dispersion for 1h, adding the obtained mixture into a reaction kettle, reacting for 12h at 160 ℃, cooling to room temperature, performing suction filtration and washing, performing vacuum drying at 90 ℃ for 6h, performing roasting at 700 ℃ for 4h, and grinding to obtain a porous carrier, namely TiO ₂-Al₂O₃;

S2, loading magnesium hydroxide on a porous carrier:

Adding 5g of porous carrier into 200mL of deionized water, performing ultrasonic dispersion for 30min, then adding 3.15g of MgCl ₂, stirring for 15min, dropwise adding 75mL of 1mol/L NaOH aqueous solution under stirring, stirring at 50 ℃ for reaction for 2h after the dropwise adding is completed, filtering, washing with deionized water, and performing vacuum drying at 80 ℃ for 4h to obtain flame-retardant particles, namely TiO ₂-Al₂O₃@Mg(OH)₂;

s3, modifying a photo-thermal agent on the flame-retardant particles:

S3-2, adding the mixed solution 2 into the mixed solution 1 under stirring, performing ultrasonic dispersion for 10min at 70 ℃ to obtain a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined reaction kettle, reacting for 8h at 175 ℃, cooling to room temperature, performing suction filtration, washing a solid product with ethanol, and performing vacuum drying for 12h at 90 ℃ to obtain functionalized flame-retardant particles, wherein the functionalized flame-retardant particles are denoted as Ti ₂-Al₂O₃@Mg(OH)₂ @Fe-CDs;

s4, loading an auxiliary agent on the functionalized flame-retardant particles:

wherein the antioxidant is antioxidant 1010, and the ultraviolet absorbent is ultraviolet absorbent UV-9 (2-hydroxy-4-methoxybenzophenone);

S4-2, adding 5g of functionalized flame-retardant particles into 100mL of impregnating solution, performing ultrasonic dispersion for 1h, then placing the particles in a supergravity packed bed (namely a rotary packed bed), treating the particles for 4h under the supergravity condition of 150 times of gravity acceleration, taking the particles out of the supergravity packed bed, standing the particles for 2h, filtering, sequentially washing the particles with acetone and ethanol, and performing vacuum drying at 60 ℃ for 12h to obtain core particles;

S5, coating a polyurethane microporous membrane on the kernel particles:

S5-1, adding 5g of PPG (polypropylene glycol), 3.5g of TDI (toluene diisocyanate) and 1.4g of hydroxypropyl silicone oil into 100mL of acetone, heating to 65 ℃ under the protection of nitrogen, then dropwise adding 0.015g of triethylene diamine, stirring and reacting for 1.5h, adding 2mL of butanediol and 0.8mL of ethylene diamine, stirring and reacting for 3h at 72 ℃, cooling to room temperature, and distilling under reduced pressure to remove acetone to obtain modified polyurethane emulsion;

S5-2, adding 5g of modified polyurethane emulsion, 2.5g of core particles and 0.56g of polyethylene glycol into a mixed solution consisting of 30mL of butanone and 30mL of DMF (N, N-dimethylformamide), stirring for 15min, stirring for reaction at 70 ℃ for 30min, standing for 15min, cooling to room temperature, centrifuging, adding the obtained solid product into 50mL of DMF, stirring for 10min, suction filtering, adding the solid product into 100mL of deionized water at 75 ℃, stirring for 4h, suction filtering, and vacuum drying the solid product for 12h at 50 ℃ to obtain the core-shell flame retardant anti-ultraviolet particles.

Example 2

the preparation method of the polyester fiber comprises the following steps:

s1, preparing a porous carrier:

S2, loading magnesium hydroxide on a porous carrier:

s3, modifying a photo-thermal agent on the flame-retardant particles:

s4, loading an auxiliary agent on the functionalized flame-retardant particles:

S5, coating a polyurethane microporous membrane on the kernel particles:

S5-2, adding 5g of modified polyurethane emulsion, 2.5g of core particles and 0.85g of polyethylene glycol into a mixed solution consisting of 30mL of butanone and 30mL of DMF (N, N-dimethylformamide), stirring for 15min, stirring for reaction at 70 ℃ for 30min, standing for 15min, cooling to room temperature, centrifuging, adding the obtained solid product into 50mL of DMF, stirring for 10min, suction filtering, adding the solid product into 100mL of deionized water at 75 ℃, stirring for 4h, suction filtering, and vacuum drying the solid product for 12h at 50 ℃ to obtain the core-shell flame retardant anti-ultraviolet particles.

Example 3

the preparation method of the polyester fiber comprises the following steps:

s1, preparing a porous carrier:

S2, loading magnesium hydroxide on a porous carrier:

s3, modifying a photo-thermal agent on the flame-retardant particles:

s4, loading an auxiliary agent on the functionalized flame-retardant particles:

S5, coating a polyurethane microporous membrane on the kernel particles:

S5-2, adding 5g of modified polyurethane emulsion, 2.5g of core particles and 1.0g of polyethylene glycol into a mixed solution consisting of 30mL of butanone and 30mL of DMF (N, N-dimethylformamide), stirring for 15min, stirring for reaction at 70 ℃ for 30min, standing for 15min, cooling to room temperature, centrifuging, adding the obtained solid product into 50mL of DMF, stirring for 10min, suction filtering, adding the solid product into 100mL of deionized water at 75 ℃, stirring for 4h, suction filtering, and vacuum drying the solid product for 12h at 50 ℃ to obtain the core-shell flame retardant anti-ultraviolet particles.

Example 4

the preparation method of the polyester fiber comprises the following steps:

1) Vacuum drying the polyester chip for 12 hours at 110 ℃, and then stirring and mixing the polyester chip with core-shell flame-retardant anti-ultraviolet particles and anti-dripping agents for 25 minutes at 600rpm to obtain a polyester mixed material;

2) Adding the polyester mixed material into a double-screw extruder, and carrying out melt extrusion at 245 ℃ to obtain melt, spinning to obtain the ultraviolet-resistant high-flame-retardance polyester fiber, wherein the spinning temperature is 265 ℃, the spinning speed is 700m/min, the drawing multiple is 2 times, and the drawing rate is 700 m/mm.

s1, preparing a porous carrier:

S2, loading magnesium hydroxide on a porous carrier:

s3, modifying a photo-thermal agent on the flame-retardant particles:

s4, loading an auxiliary agent on the functionalized flame-retardant particles:

S4-2, adding 5g of functionalized flame-retardant particles into 100mL of impregnating solution, performing ultrasonic dispersion for 1h, then placing the particles in a supergravity packed bed (namely a rotary packed bed), treating the particles for 5h under the supergravity condition of 100 times of gravity acceleration, taking the particles out of the supergravity packed bed, standing the particles for 2h, filtering, sequentially washing the particles with acetone and ethanol, and performing vacuum drying at 60 ℃ for 12h to obtain core particles;

S5, coating a polyurethane microporous membrane on the kernel particles:

S5-1, adding 5g of PPG (polypropylene glycol), 3.5g of TDI (toluene diisocyanate) and 1.4g of hydroxypropyl silicone oil into 100mL of acetone, heating to 68 ℃ under the protection of nitrogen, then dropwise adding 0.015g of triethylene diamine, stirring and reacting for 1.5h, adding 2mL of butanediol and 0.8mL of ethylene diamine, stirring and reacting for 3h at 75 ℃, cooling to room temperature, and distilling under reduced pressure to remove acetone to obtain modified polyurethane emulsion;

S5-2, adding 5g of modified polyurethane emulsion, 2.5g of core particles and 0.56g of polyethylene glycol into a mixed solution consisting of 30mL of butanone and 30mL of DMF (N, N-dimethylformamide), stirring for 15min, stirring for reaction for 30min at 72 ℃, standing for 15min, cooling to room temperature, centrifugally separating, adding the obtained solid product into 50mL of DMF, stirring for 10min, suction filtering, adding the solid product into 100mL of deionized water at 75 ℃, stirring for 4h, suction filtering, and vacuum drying the solid product for 12h at 50 ℃ to obtain the core-shell flame retardant anti-ultraviolet particles.

Comparative example 1

This comparative example differs from example 1 only in that:

the core-shell type flame-retardant ultraviolet-resistant particle is prepared by the following method:

S1, preparing a porous carrier, wherein the steps are the same as those of the embodiment 1;

S2, loading magnesium hydroxide on a porous carrier to prepare flame-retardant particles, wherein the steps are the same as those of the embodiment 1;

s3, loading an auxiliary agent on the flame-retardant particles:

S3-1, adding an antioxidant and an ultraviolet absorbent into acetone, and uniformly stirring to prepare an auxiliary agent impregnating solution with the concentration of the antioxidant of 10g/L and the concentration of the ultraviolet absorbent of 6 g/L;

S3-2, adding 5g of flame-retardant particles into 100mL of impregnating solution, performing ultrasonic dispersion for 1h, placing the mixture in a supergravity packed bed (namely a rotary packed bed), treating the mixture for 4h under the supergravity condition of 150 times of gravity acceleration, taking the mixture out of the supergravity packed bed, standing the mixture for 2h, filtering, sequentially washing acetone and ethanol, and performing vacuum drying at 60 ℃ for 12h to obtain core particles;

S4, coating a polyurethane microporous membrane on the core particles, wherein the steps are the same as in the example 1.

Comparative example 2

This comparative example differs from example 1 only in that no ferric citrate was added in step S3-1.

Comparative example 3

This comparative example differs from example 1 only in that indocyanine green was not added in step S3-1.

Comparative example 4

This comparative example differs from example 1 only in that:

The step S1 of preparing the core-shell flame-retardant ultraviolet-resistant particles is as follows:

10g of AI (NO ₃)₃·9H₂ O, 0.25g of hexadecyl trimethyl ammonium bromide are added into 150mL of deionized water, 7.9g of ammonium bicarbonate is added after stirring for 10min, 50mL of n-butanol is added after stirring for 30min, ultrasonic dispersion is carried out for 1h, the obtained mixture is added into a reaction kettle for reaction for 12h at 160 ℃, cooling is carried out to room temperature, suction filtration and washing are carried out, vacuum drying is carried out at 90 ℃ for 6h, roasting is carried out at 700 ℃ for 4h, and the porous carrier is obtained after grinding.

Comparative example 5

The preparation raw materials of the ultraviolet-resistant high-flame-retardance polyester fiber comprise, by weight, 100 parts of polyester chips, 39 parts of core-shell ultraviolet-resistant particles, 3 parts of magnesium hydroxide and 3 parts of anti-dripping agent, wherein the anti-dripping agent is triallyl isocyanurate, and the preparation method of the polyester fiber comprises the following steps:

1) Vacuum drying the polyester chip for 12 hours at 110 ℃, and then stirring and mixing the polyester chip with core-shell type anti-ultraviolet particles, magnesium hydroxide and anti-melting drops for 25 minutes at 600rpm to obtain a polyester mixed material;

The core-shell type anti-ultraviolet particle is prepared by the following steps:

s2, modifying a photo-thermal agent on a porous carrier:

s2-1, adding 5g of porous carrier and 1225mg of ferric citrate into 100mL of deionized water with the temperature of 70 ℃ for ultrasonic dispersion for 30min to obtain a mixed solution 1, adding 900mg of glucose, 407mg of 2',7' -dichloro-dihydro-fluorescein diacetate, 244mg of 4-dimethylaminopyridine and 465mg of indocyanine green into a mixed solvent composed of 40mL of ethanol and 60mL of deionized water, and stirring for 15min to obtain a mixed solution 2;

S2-2, adding the mixed solution 2 into the mixed solution 1 under stirring, performing ultrasonic dispersion for 10min at 70 ℃ to obtain a precursor solution, transferring the precursor solution into a polytetrafluoroethylene-lined reaction kettle, reacting for 8h at 175 ℃, cooling to room temperature, performing suction filtration, washing a solid product with ethanol, and performing vacuum drying for 12h at 90 ℃ to obtain functionalized particles;

S3, loading an auxiliary agent on the functionalized particles:

s3-1, adding an antioxidant and an ultraviolet absorbent into acetone, and uniformly stirring to prepare an auxiliary agent impregnating solution with the concentration of the antioxidant of 10g/L and the concentration of the ultraviolet absorbent of 6g/L, wherein the antioxidant is antioxidant 1010, and the ultraviolet absorbent is ultraviolet absorbent UV-9 (2-hydroxy-4-methoxybenzophenone);

s3-2, adding 5g of functionalized particles into 100mL of impregnating solution, performing ultrasonic dispersion for 1h, placing the mixture in a supergravity packed bed (namely a rotary packed bed), treating the mixture for 4h under the supergravity condition of 150 times of gravity acceleration, taking the mixture out of the supergravity packed bed, standing the mixture for 2h, filtering, sequentially washing acetone and ethanol, and performing vacuum drying at 60 ℃ for 12h to obtain core particles;

s4, coating a polyurethane microporous membrane on the core particles to obtain the core-shell type anti-ultraviolet particles, wherein the steps are the same as in the example 1.

Comparative example 6

The ultraviolet-resistant high-flame-retardance polyester fiber comprises the following raw materials in parts by weight: the anti-drip agent is triallyl isocyanurate. The preparation method of the polyester fiber comprises the following steps:

1) Vacuum drying the polyester chip at 110 ℃ for 12 hours, and stirring and mixing the polyester chip with the core particles and the anti-dripping agent at 600rpm for 25 minutes to obtain a polyester mixed material;

Wherein the core particle was prepared in the same manner as in example 1.

1. Characterization of Performance

1. Referring to FIG. 1, it can be seen that Mg (OH) ₂ and Fe-CDs were successfully supported on TiO ₂-Al₂O₃ for the infrared absorption spectra of the porous support (TiO ₂-Al₂O₃) and the functionalized flame retardant particles [ TiO ₂-Al₂O₃@Mg(OH)₂ @ Fe-CDs ] prepared in example 1.

2. Photothermal properties

2-1, Adding the functionalized flame-retardant particles and deionized water into a container, performing ultrasonic dispersion for 20min to prepare a dispersion liquid with the concentration of 1.0mg/mL, irradiating the dispersion liquid for 10min by using an ultraviolet light source with the wavelength of 350nm (the distance between the light source and the dispersion liquid is 10 cm) and controlling the power density of the light source to be 1.0W/cm ², wherein the ambient temperature is 25 ℃, and recording 1 time of temperature every 1min by using an infrared thermal imager to make a temperature-time curve.

Referring to fig. 2, to test the temperature-time curves of the flame retardant particles [ TiO ₂-Al₂O₃@Mg(OH)₂ ] and the functionalized flame retardant particles [ TiO ₂-Al₂O₃@Mg(OH)₂ @ Fe-CDs ] prepared in example 1, it can be seen that TiO ₂-Al₂O₃@Mg(OH)₂ @ Fe-CDs has significant photo-thermal properties, whereas TiO ₂-Al₂O₃@Mg(OH)₂ does not have photo-thermal properties, and comparison of the two can indicate that the photo-thermal properties are derived from modified carbon dots (Fe-CDs). Further tests show that when the ultraviolet light source is continuously applied (12 h), the temperature is stable after reaching about 84 ℃, the temperature is basically not increased any more, and the reasons are analyzed, mainly because of the limitation of the light source power, the balance of heat generation and heat dissipation, the photo-thermal efficiency of the functional flame-retardant particles and the like, and the upper limit of the temperature caused by photo-thermal is not always increased. In order to further test the photo-thermal effect of the core-shell flame-retardant and ultraviolet-resistant particles added into the polyester fiber, the polyester fiber prepared in the test example 1 is continuously irradiated for 12 hours by using an ultraviolet light source (controlling the power density of the light source to be 1.0W/cm ² and the distance between the ultraviolet light source and the polyester fiber to be 50 cm), the result shows that the highest temperature is 89 ℃, the addition amount of the core-shell flame-retardant and ultraviolet-resistant particles is adjusted to be 20 parts and 60 parts on the basis of the example 1, the highest temperature obtained by the test is 76 ℃ and 97 ℃ respectively, which indicates that the prepared polyester fiber also shows photo-thermal performance after being added into the polyester fiber, and the temperature caused by photo-thermal is also limited and cannot be always increased.

2-2, Adding the core-shell flame-retardant ultraviolet-resistant particles in examples 1-4 and comparative examples 2-3 into a container, preparing a dispersion liquid with the concentration of 1.0mg/mL by deionized water, irradiating the dispersion liquid for 10min by using an ultraviolet light source with the wavelength of 350nm (the light source is positioned right above and is spaced from the dispersion liquid by 10 cm), controlling the power density of the light source to be 1.0W/cm ², using an infrared thermal imager, detecting the temperature of the system, preparing, characterizing and performing [ J ]. Fine chemical engineering, 2024, 41 (8): 1745-1753 ], and calculating the light-heat conversion efficiency eta (%) according to the following formula:

;

Wherein h is the heat transfer coefficient, unit W/(m ². K), S is the container surface area, unit m ²;T_m is the steady-state highest temperature, unit K, T _r is the ambient room temperature, unit K, Q ₀ is the reference energy input by deionized water without adding functional flame-retardant particles and the container, unit J, P is the light source power, unit W, and A ₃₅₀ is the absorbance of the dispersion at 350 nm.

The results of the photothermal conversion efficiency test are shown in table 1 below:

TABLE 1

	Example 1	Example 2	Example 3	Example 4	Comparative example 2	Comparative example 3
							Photo-thermal conversion efficiency η (%)	38.1	40.6	42.0	37.7	31.6	30.3

From the results of examples 1-3, it can be seen that the photo-thermal conversion efficiency exhibited by the core-shell flame retardant and ultraviolet resistant particles increases to some extent as the content of the porogen polyethylene glycol increases, due to the increase in the content of the porogen, the porosity of the polyurethane microporous membrane increases. Comparison of comparative examples 2-3 with example 1 shows that doping of Fe in the photothermal agent (carbon dot) and addition of indocyanine green can improve the photothermal conversion efficiency.

3. Ultraviolet absorption Property

Referring to fig. 4, which shows the uv-vis absorption spectra of the core-shell type flame retardant uv-resistant particles prepared in example 1, comparative example 1 and comparative example 4, it can be seen that example 1 has a wide uv absorption region, and the uv absorption capacities of comparative example 1 and comparative example 4 are significantly reduced, which means that both the photothermal agent and TiO ₂ in the core-shell type flame retardant uv-resistant particles can improve uv absorption performance.

4. Ultraviolet absorber Release Properties

The testing method comprises the following steps: 10g of the core-shell flame-retardant ultraviolet-resistant particles prepared in example 1 are packed by a filter bag and then placed in a glass container, and the following operations are carried out every 12 hours:

(1) Adding 50mL of acetone into a dark group (No Light), soaking for 60min, washing with acetone for 3 times, taking out, collecting washing liquid and soaking liquid, combining, measuring total volume of the liquid, and detecting the concentration of ultraviolet absorbent UV-9 by gas chromatography to obtain release amount;

(2) Adding 50mL of acetone into the illumination group (350 nm Light), soaking for 60min under 350nm illumination (Light source is positioned right above 20cm and power density is 1.0W/cm ²), then washing 3 times with acetone, taking out, collecting washing liquid and soaking liquid, combining, measuring total volume of liquid, detecting concentration of ultraviolet absorbent UV-9 by gas chromatography, and obtaining release amount;

The two groups were each tested for 180h and a release profile was plotted with the cumulative value of the percent released (Accumulated Release) on the ordinate and the treatment time on the abscissa. Wherein the percentage release cumulative value k= Q _t represents the cumulative amount of released during t time, Q ₀ represents the total amount of the ultraviolet absorber UV-9, and Q ₀ is obtained by subtracting the total mass of the ultraviolet absorber UV-9 in the acetone in step S4-1 of example 1 from the mass of the ultraviolet absorber UV-9 remaining in the immersed auxiliary agent immersion liquid.

The test results are shown in fig. 5, and it can be seen that both groups show better slow release performance, and the release amount of the ultraviolet absorbent UV-9 is obviously improved after illumination is increased, which proves that the core-shell flame-retardant ultraviolet-resistant particles can promote the release of the ultraviolet absorbent in the core-shell flame-retardant ultraviolet-resistant particles under the illumination of ultraviolet light, and the self-adaptive regulation and control performance of the core-shell flame-retardant ultraviolet-resistant particles is verified.

2. Application Performance test

The polyester fibers prepared in examples 1 to 4 and comparative examples 1 to 6 were subjected to the following performance test:

1. Anti-ultraviolet properties

The ultraviolet transmittance was measured according to the standard GB/T18830-2009, and the measurement results are shown in the following Table 2, FIG. 6 and FIG. 7:

TABLE 2

	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
											UVA transmittance/%	0.45	0.42	0.38	0.47	18.2	2.5	3.1	9.7	0.48	5.7
UVB transmittance/%	0.16	0.14	0.11	0.19	4.7	0.46	0.58	2.5	0.20	0.92

From the test results, examples 1 to 4 have excellent anti-ultraviolet performance, and the content of the pore-forming agent in examples 2 and 3 is increased, so that the exposure of the anti-ultraviolet active component is increased, and the anti-ultraviolet performance is enhanced to a certain extent. The unmodified carbon dots in the core-shell flame-retardant anti-ultraviolet particles of the comparative example 1 have obviously reduced anti-ultraviolet performance, the results of the comparative example 2 and the comparative example 3 show that the doping of Fe in the carbon dots and the addition of indocyanine green can improve the anti-ultraviolet performance, the anti-ultraviolet performance is greatly reduced due to the undoped TiO ₂ in the comparative example 4, the anti-ultraviolet performance of the comparative example 5 is not obviously changed, the core particles are difficult to uniformly disperse due to the uncoated polyurethane microporous membrane in the comparative example 6, the performance of active components in the active components is influenced, and the anti-ultraviolet performance is obviously reduced.

2. Flame retardant Properties

With reference to the standard GB/T2406.2-2009 test, the test results are shown in Table 3 and FIG. 8 below:

TABLE 3 Table 3

	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
											Limiting Oxygen Index (LOI)/%	39.4	38.7	38.2	39.1	38.2	39.1	39.3	38.6	30.3	30.9

3. Breaking strength

The breaking strength of the polyester fibers was measured with reference to the standard GB/T14344-2022 chemical fiber filament tensile property test method. The test results are shown in table 4 and fig. 9 below:

TABLE 4 Table 4

	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
											Breaking Strength (cN/detx)	3.52	3.41	3.30	3.49	3.50	3.54	3.52	2.91	3.23	3.12

The breaking strength after aging was measured by radiating a polyester fiber with ultraviolet rays having a wavelength of 350nm for 300 hours (distance between a light source and a sample: 30cm, power: 40W), measuring the breaking strength, and calculating the retention of the breaking strength = (breaking strength after light irradiation/breaking strength before light irradiation) ×100%. The test results are shown in table 5 and fig. 10 below:

TABLE 5

	Example 1	Example 2	Example 3	Example 4	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6
											Retention of breaking Strength (%)	96.8	96.1	95.5	96.3	84.2	90.6	88.7	90.5	95.7	89.4

From the test results, it can be seen that examples 1 to 4 have excellent ultraviolet aging resistance, and that comparative examples 1 to 4 and comparative example 6 have various degrees of deterioration in ultraviolet aging resistance.

Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.

Claims

1. The ultraviolet-resistant high-flame-retardance polyester fiber is characterized by comprising the following raw materials in parts by weight: 100 parts of polyester chips, 20-60 parts of core-shell flame-retardant ultraviolet-resistant particles and 2-4.5 parts of anti-drip agent; the core-shell type flame-retardant ultraviolet-resistant particle is prepared by the following method:

2. The anti-ultraviolet high-flame-retardant polyester fiber according to claim 1, wherein the anti-dripping agent is at least one of melamine, benzoguanamine and triallyl isocyanurate, the antioxidant is at least one of antioxidant 1010, antioxidant 618, antioxidant 1076 and antioxidant 1098, and the ultraviolet absorber is at least one of UV-P, UV-1, UV-9, UVBP-4, UV-234 and UVP-327.

3. The anti-ultraviolet high-flame-retardant polyester fiber according to claim 1, wherein the core-shell flame-retardant anti-ultraviolet particles are prepared by the following method:

4. The ultraviolet-resistant high-flame-retardant polyester fiber according to claim 3, wherein the step S1 is specifically:

5. The ultraviolet-resistant high-flame-retardant polyester fiber according to claim 3, wherein the step S2 is characterized in that a porous carrier is dispersed in deionized water, mgCl ₂ is added, an aqueous solution of NaOH is added dropwise, the mixture is stirred and reacted for 1 to 4 hours at a temperature of between 40 and 60 ℃ after the dropwise addition, and the mixture is filtered, washed and dried to obtain flame-retardant particles.

6. The ultraviolet-resistant high-flame-retardant polyester fiber according to claim 3, wherein the step S3 is specifically:

7. The ultraviolet-resistant high-flame-retardant polyester fiber according to claim 3, wherein the step S4 is specifically:

8. The ultraviolet-resistant high-flame-retardant polyester fiber according to claim 3, wherein the step S5 is specifically:

9. The ultraviolet resistant high flame retardant polyester fiber according to claim 3, wherein the core-shell flame retardant ultraviolet resistant particles are prepared by the following method:

s1, preparing a porous carrier:

S2, loading magnesium hydroxide on a porous carrier:

s3, modifying a photo-thermal agent on the flame-retardant particles:

s4, loading an auxiliary agent on the functionalized flame-retardant particles:

S5, coating a polyurethane microporous membrane on the kernel particles:

10. A method for preparing the ultraviolet-resistant high-flame-retardant polyester fiber according to any one of claims 1 to 9, comprising the following steps: