阅读说明：本技术 一种有机蒙脱土增韧改性pet抗紫外老化纤维及制法 (Organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and preparation method thereof ) 是由 廖颖 曹财明 陈智水 于 2021-09-22 设计创作，主要内容包括：本发明涉及PET纤维技术领域,且公开了一种有机蒙脱土增韧改性PET抗紫外老化纤维,氯化蒙脱土与聚乙二醇反应,得到聚乙二醇改性蒙脱土,其与丁二酸酐反应,得到羧基化聚乙二醇改性蒙脱土,再经过氯化亚砜的修饰,得到酰氯基聚乙二醇改性蒙脱土,进一步与苯并三唑衍生物反应,得到苯并三唑基聚乙二醇改性蒙脱土,蒙脱土可以吸收应力,聚乙二醇长链可以增强PET基体的柔韧性,进一步提高了复合PET纤维的韧性,同时,蒙脱土可以吸收和散射紫外光,而苯并三唑基团可以将高能量的紫外光转换成热能,通过结合蒙脱土、聚乙二醇和苯并三唑的优势,大大的提高了复合PET纤维的力学、抗紫外等综合性能,进一步拓展了PET的应用领域。(The invention relates to the technical field of PET (polyethylene glycol terephthalate) fibers, and discloses an organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber, wherein chlorinated montmorillonite reacts with polyethylene glycol to obtain polyethylene glycol modified montmorillonite, the polyethylene glycol modified montmorillonite reacts with succinic anhydride to obtain carboxylated polyethylene glycol modified montmorillonite, the carboxylated polyethylene glycol modified montmorillonite is modified by thionyl chloride to obtain acyl chloride-based polyethylene glycol modified montmorillonite, the acyl chloride-based polyethylene glycol modified montmorillonite further reacts with a benzotriazole derivative to obtain benzotriazole-based polyethylene glycol modified montmorillonite, the montmorillonite can absorb stress, the polyethylene glycol long chain can enhance the flexibility of a PET matrix, the toughness of the composite PET fiber is further improved, meanwhile, the montmorillonite can absorb and scatter ultraviolet light, the benzotriazole group can convert high-energy ultraviolet light into heat energy, and the mechanical property, the ultraviolet resistance and the aging resistance of the composite PET fiber are greatly improved by combining the advantages of montmorillonite, the polyethylene glycol and the benzotriazole, The comprehensive properties of ultraviolet resistance and the like further expand the application field of PET.)

1. An organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber is characterized in that: the preparation method of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber comprises the following steps:

(1) adding nano-montmorillonite and 3-chloropropyl triethoxysilane with the mass ratio of 100:180-400 into a deionized water solvent, ultrasonically dispersing uniformly, adjusting the pH of the solution to 6-8 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 50-70 ℃ for reaction for 2-6h, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;

(2) adding chlorinated montmorillonite into an absolute ethyl alcohol solvent, performing ultrasonic dispersion uniformly, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring in an ice-water bath, adding polyethylene glycol for substitution reaction, centrifuging after the reaction is finished, performing reduced pressure distillation, filtering and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding polyethylene glycol modified montmorillonite into a toluene solvent, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, transferring to an oil bath pot, raising the temperature to perform ring-opening esterification reaction, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding carboxylated polyethylene glycol modified montmorillonite into a toluene solvent, adding thionyl chloride after ultrasonic dispersion is uniform, transferring the mixture into an oil bath pot, raising the temperature to perform acyl chlorination reaction, and after the reaction is finished, performing reduced pressure distillation, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) prepared from o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powderReacting to obtain benzotriazole derivative with molecular formula C₁₂H₉N₃O₂；

(6) Adding acyl chloride polyethylene glycol modified montmorillonite into a trichloromethane solvent, adding a benzotriazole derivative and sodium hydroxide after uniform ultrasonic dispersion, transferring the mixture into an oil bath pot for esterification, and centrifuging, washing and drying after the reaction is finished to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding PET and benzotriazole-based polyethylene glycol modified montmorillonite into a dichloromethane solvent, stirring to form a uniform spinning solution, pouring the uniform spinning solution into a high-speed spinning machine for spinning, transferring the uniform spinning solution onto a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

2. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the mass ratio of the chlorinated montmorillonite to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol in the step (2) is 100:40-80:0.6-1.4: 260-.

3. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the temperature of the substitution reaction in the step (2) is 15-35 ℃, and the reaction is carried out for 20-30h under the condition of constant-temperature stirring in the nitrogen atmosphere.

4. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride in the step (3) is 100: 25-50.

5. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the temperature of the ring opening esterification reaction in the step (3) is 100-120 ℃, and the reaction is carried out for 4-10h under constant temperature reflux in a nitrogen atmosphere.

6. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride in the step (4) is 100: 120-280.

7. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the temperature of the acyl chlorination reaction in the step (4) is 70-90 ℃, and the reaction is carried out for 20-30h under the stirring of nitrogen atmosphere.

8. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: in the step (6), the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:15-35: 6-12.

9. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the temperature of the esterification reaction in the step (6) is 15-35 ℃, and the esterification reaction is carried out for 2-6h under the condition of constant-temperature stirring in the nitrogen atmosphere.

10. The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber as claimed in claim 1, which is characterized in that: the mass ratio of the PET to the benzotriazole-based polyethylene glycol modified montmorillonite in the step (7) is 100: 2-6.

Technical Field

The invention relates to the technical field of PET (polyethylene terephthalate) fibers, in particular to an organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and a preparation method thereof.

Background

With the continuous damage of the atmospheric layer, more and more ultraviolet rays are projected on the surface of the earth, the high-energy ultraviolet rays irradiate the skin of human being for a long time and cause great harm to the health of people, so that the ultraviolet-resistant fabric is gradually concerned, and the research heat is aroused in the world, and the polyester fiber (PET) has the characteristics of good wrinkle resistance, high shape retention, strong elasticity and the like, and has great application value in the field of clothing fiber, but the polyester fiber matrix does not have the ultraviolet resistance and can not shield the ultraviolet rays, the strength of the polyester fiber is not high enough, the phenomena of thread breakage, pulling crack and the like are easy to occur, the further development of the polyester fiber is greatly limited, so that the traditional polyester fiber is modified at will, and the filling modification is a common polymer modification means, namely, the epoxy resin and the filling modification means are common polymer modification means, Organic polymer materials such as PET and the like are filled with inorganic nano materials such as titanium dioxide, montmorillonite and the like with excellent performances such as high strength, ultraviolet absorption and the like, or organic polymer materials such as polyvinyl alcohol, polyethylene glycol and the like with toughening and reinforcing performances, and the effect of improving the comprehensive performance of the organic polymer materials is achieved by combining the advantages of the organic and inorganic materials.

Montmorillonite, a nano-dimension silicate sheet layer with negative charges on the surface, has good adsorbability, dimensional stability and gas barrier property, and in recent years, the application of montmorillonite as a functional reinforcing filler is gradually developed by people, but the montmorillonite on the nano layer surface is easy to agglomerate, and can not be stably dispersed when the addition amount in the organic polymer material matrix is higher, moreover, the ultraviolet shielding performance of the montmorillonite is relatively common, and the performance can be greatly improved without adding a small amount of montmorillonite, therefore, montmorillonite needs to be modified, the surface of montmorillonite is organically modified by using a silane coupling agent, and then an organic functional group with special performance is introduced through an active functional group of the silane coupling agent, can improve the strength and the breadth of the montmorillonite used as the functional reinforcing filler and provide great convenience for the further application of the montmorillonite.

Technical problem to be solved

Aiming at the defects of the prior art, the invention provides an organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and a preparation method thereof, and solves the problems that the traditional polyester fiber is poor in strength and does not have anti-ultraviolet aging performance.

(II) technical scheme

In order to achieve the purpose, the invention provides the following technical scheme: the preparation method of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber comprises the following steps:

(1) adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane with the mass ratio of 100: 180-;

(2) adding an absolute ethyl alcohol solvent and chlorinated montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, placing the mixture in an ice-water bath, stirring for 5-15min, continuously adding polyethylene glycol into the system for substitution reaction, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck bottle, ultrasonically dispersing uniformly, continuously adding succinic anhydride, transferring into an oil bath pot, raising the temperature to perform ring-opening esterification reaction, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck bottle, ultrasonically dispersing uniformly, then continuously adding thionyl chloride, transferring into an oil bath pot, raising the temperature to perform acyl chlorination reaction, and after the reaction is finished, distilling under reduced pressure to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C₁₂H₉N₃O₂；

(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, stirring until the benzotriazole derivative and the sodium hydroxide are completely dissolved, carrying out esterification reaction, and centrifuging, washing and drying after the reaction is finished to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite into a reactor, stirring to form a uniform spinning solution, pouring the uniform spinning solution into a high-speed spinning machine for spinning, transferring the uniform spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

Preferably, the mass ratio of the montmorillonite chloride, the potassium hydroxide, the n-tetrabutylammonium sulfate and the polyethylene glycol in the step (2) is 100:40-80:0.6-1.4: 260-540.

Preferably, the temperature of the substitution reaction in the step (2) is 15-35 ℃, and the reaction is carried out for 20-30h under the condition of constant-temperature stirring in the nitrogen atmosphere.

Preferably, the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride in the step (3) is 100: 25-50.

Preferably, the temperature of the ring opening esterification reaction in the step (3) is 100-120 ℃, and the reaction is carried out for 4-10h under constant temperature reflux in a nitrogen atmosphere.

Preferably, the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride in the step (4) is 100: 120-280.

Preferably, the temperature of the acyl chlorination reaction in the step (4) is 70-90 ℃, and the reaction is carried out for 20-30h under the stirring of nitrogen atmosphere.

Preferably, in the step (6), the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:15-35: 6-12.

Preferably, the temperature of the esterification reaction in the step (6) is 15-35 ℃, and the reaction is carried out for 2-6h under the condition of constant-temperature stirring in the nitrogen atmosphere.

Preferably, the mass ratio of the PET to the benzotriazole-based polyethylene glycol modified montmorillonite in the step (7) is 100: 2-6.

(III) advantageous technical effects

Compared with the prior art, the invention has the following beneficial technical effects:

the surface of montmorillonite modified by 3-chloropropyltriethoxysilane contains a large amount of chlorine atoms, and the montmorillonite is subjected to substitution reaction with hydroxyl in polyethylene glycol under the combined action of a catalyst n-tetrabutylammonium sulfate and acid-binding agent potassium hydroxide to obtain polyethylene glycol modified montmorillonite, the residual hydroxyl in the molecular chain of the polyethylene glycol modified montmorillonite can be subjected to ring-opening esterification reaction with succinic anhydride to obtain carboxylated polyethylene glycol modified montmorillonite, carboxyl in the carboxylated polyethylene glycol modified montmorillonite is modified into acyl chloride through modification of thionyl chloride to obtain acyl chloride-based polyethylene glycol modified montmorillonite, and the acyl chloride-based polyethylene glycol modified montmorillonite is further subjected to esterification reaction with para-position phenolic hydroxyl in a benzotriazole derivative under the action of acid-binding agent sodium hydroxide to obtain benzotriazole-based polyethylene glycol modified montmorillonite, and is modified by chemical bonds, organic molecules such as chlorine atoms, polyethylene glycol, carboxyl, acyl chloride groups, benzotriazole groups and the like are covalently grafted on the surface of the montmorillonite, and the application range of the montmorillonite is further improved by combining the excellent properties of the organic molecules, so that convenience is brought to the further application of the montmorillonite.

The organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber is prepared by adding benzotriazole-based polyethylene glycol modified montmorillonite into a PET matrix, spinning through a high-speed spinning machine to obtain the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber, wherein the high strength and dimensional stability of montmorillonite enable the PET matrix to absorb a large amount of stress when being subjected to external force, and cracks generated by stress fracture can be prevented from further expanding, so that the mechanical properties such as tensile strength, impact strength and the like of the composite PET fiber are enhanced, polyethylene glycol long chains grafted on the surface of montmorillonite have good flexibility, and after forming a mutual winding network structure with the PET matrix, the flexibility of the PET matrix can be greatly enhanced, and when being subjected to external force, the flexible network can absorb a large amount of deformation work, so that the toughness of the composite PET fiber is further improved, in addition, montmorillonite is used as a silicate mineral, can absorb ultraviolet light, and can scatter high-energy ultraviolet light to the air through a higher specific surface area, so that the ultraviolet resistance of the composite PET fiber is improved to a certain extent, meanwhile, a benzotriazole group grafted on the surface of montmorillonite can form a chelated six-membered ring in a molecule under the irradiation of ultraviolet light, namely, the ultraviolet light with high energy is converted into heat energy required in chemical reaction, so that the ultraviolet resistance of the composite PET fiber is further improved, by combining the advantages of montmorillonite, polyethylene glycol and benzotriazole, the comprehensive performances of the composite PET fiber, such as mechanics, ultraviolet resistance and the like, are greatly improved, and the application field of PET is further expanded.

Drawings

FIG. 1 is a schematic representation of the reaction of chlorinated montmorillonite and polyethylene glycol.

FIG. 2 is a schematic diagram of the reaction of polyethylene glycol modified montmorillonite and succinic anhydride.

FIG. 3 is a schematic diagram of the reaction of carboxylated polyethylene glycol modified montmorillonite and thionyl chloride.

FIG. 4 is a reaction scheme of acyl chloride polyethylene glycol modified montmorillonite and benzotriazole derivative.

Detailed Description

To achieve the above object, the present invention provides the following embodiments and examples: an organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber is prepared by the following steps:

(1) adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane with the mass ratio of 100: 180-;

(2) adding an absolute ethanol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring in an ice-water bath for 5-15min, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:40-80:0.6-1.4:260 and 540, reacting at 15-35 ℃ for 20-30h in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:25-50, transferring the mixture into an oil bath pot, reacting for 4-10h at the temperature of 120 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, continuing adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:120-280, transferring the mixture into an oil bath pot, stirring and reacting for 20-30h at 70-90 ℃ in a nitrogen atmosphere, and after the reaction is finished, carrying out reduced pressure distillation to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C₁₂H₉N₃O₂；

(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:15-35:6-12, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 2-6h at 15-35 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:2-6 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution onto a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

Example 1

(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:180 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 6 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 50 ℃ for reaction for 2 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;

(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring for 5min in an ice-water bath, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:40:0.6:260, reacting for 20h at 15 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:25, transferring the mixture into an oil bath pot, reacting for 4 hours at 100 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:120, transferring the mixture into an oil bath pot, carrying out stirring reaction for 20 hours at 70 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C₁₂H₉N₃O₂；

(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:15:6, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 2 hours at 15 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:2 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

Example 2

(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:240 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 7 by hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 55 ℃ for reaction for 3 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;

(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring for 6min in an ice-water bath, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:50:0.8:330, reacting for 22h at 20 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:30, transferring the mixture into an oil bath pot, reacting for 5 hours at 105 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:160, transferring the mixture into an oil bath pot, carrying out stirring reaction for 22 hours at 75 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C₁₂H₉N₃O₂；

(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:20:7.5, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 3 hours at 20 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:3 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

Example 3

(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:290 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 7 by hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 60 ℃ for reaction for 4 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;

(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, ultrasonically dispersing uniformly, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring for 10min in an ice-water bath, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:60:1:400, reacting for 25h at 25 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:38, transferring the mixture into an oil bath pot, reacting for 6 hours at 110 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:200, transferring the mixture into an oil bath pot, carrying out stirring reaction for 25 hours at 80 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C₁₂H₉N₃O₂；

(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:25:9, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 4 hours at 25 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:4 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

Example 4

(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:350 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 7 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 65 ℃ for reaction for 5 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;

(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring in an ice-water bath for 12min, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:70:1.2:470, reacting for 28h at 30 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:44, transferring the mixture into an oil bath pot, reacting for 8 hours at 115 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:240, transferring the mixture into an oil bath pot, carrying out stirring reaction for 28 hours at 85 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C₁₂H₉N₃O₂；

(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:30:10.5, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 5 hours at 30 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:5 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

Example 5

(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:400 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 8 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 70 ℃ for reacting for 6 hours, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;

(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, uniformly dispersing by ultrasonic, adding potassium hydroxide and n-tetrabutylammonium sulfate, stirring for 15min in an ice-water bath, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:80:1.4:540, reacting for 30h at 35 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:50, transferring the mixture into an oil bath pot, reacting for 10 hours at 120 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, ultrasonically dispersing uniformly, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:280, transferring the mixture into an oil bath pot, stirring and reacting for 30 hours at 90 ℃ in a nitrogen atmosphere, and after the reaction is finished, distilling under reduced pressure to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) prepared from o-nitroaniline, sodium nitrite, resorcinol, and hydrogen oxygenSodium hydroxide reacts with zinc powder to obtain benzotriazole derivative with molecular formula of C₁₂H₉N₃O₂；

(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:35:12, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 6 hours at 35 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:6 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

Comparative example 1

(1) Adding a deionized water solvent, nano-montmorillonite and 3-chloropropyl triethoxysilane in a mass ratio of 100:120 into a three-necked bottle, ultrasonically dispersing uniformly, adjusting the pH of the solution to 6 by using hydrochloric acid, transferring the solution into an oil bath pot, stirring at a constant temperature of 50 ℃ for reaction for 1 hour, centrifuging, washing and drying the product to obtain chlorinated montmorillonite;

(2) adding an absolute ethyl alcohol solvent and montmorillonite chloride into a three-neck flask, ultrasonically dispersing uniformly, adding potassium hydroxide and n-tetrabutylammonium sulfate, placing the mixture into an ice water bath, stirring for 2min, continuously adding polyethylene glycol into the system for substitution reaction, wherein the mass ratio of the montmorillonite chloride to the potassium hydroxide to the n-tetrabutylammonium sulfate to the polyethylene glycol is 100:30:0.4:190, reacting for 18h at 15 ℃ in a nitrogen atmosphere, centrifuging after the reaction is finished, distilling under reduced pressure to remove the solvent, filtering, purifying and drying to obtain polyethylene glycol modified montmorillonite;

(3) adding a toluene solvent and polyethylene glycol modified montmorillonite into a three-neck flask, uniformly dispersing by ultrasonic, continuously adding succinic anhydride, wherein the mass ratio of the polyethylene glycol modified montmorillonite to the succinic anhydride is 100:18, transferring the mixture into an oil bath pot, reacting for 3 hours at 100 ℃ in a nitrogen atmosphere, filtering, washing, centrifuging and drying a product to obtain carboxylated polyethylene glycol modified montmorillonite;

(4) adding a toluene solvent and carboxylated polyethylene glycol modified montmorillonite into a three-neck flask, carrying out uniform ultrasonic dispersion, then continuously adding thionyl chloride, wherein the mass ratio of the carboxylated polyethylene glycol modified montmorillonite to the thionyl chloride is 100:80, transferring the mixture into an oil bath pot, carrying out stirring reaction for 18 hours at 70 ℃ in a nitrogen atmosphere, carrying out reduced pressure distillation after the reaction is finished to remove the solvent, washing and drying to obtain acyl chlorinated polyethylene glycol modified montmorillonite;

(5) reacting o-nitroaniline, sodium nitrite, resorcinol, sodium hydroxide and zinc powder to obtain the benzotriazole derivative with the molecular formula of C₁₂H₉N₃O₂；

(6) Adding a trichloromethane solvent and acyl chloride polyethylene glycol modified montmorillonite into a three-necked bottle, ultrasonically dispersing uniformly, adding a benzotriazole derivative and sodium hydroxide, wherein the mass ratio of the acyl chloride polyethylene glycol modified montmorillonite to the benzotriazole derivative to the sodium hydroxide is 100:10:4.5, stirring until the acyl chloride polyethylene glycol modified montmorillonite, the benzotriazole derivative and the sodium hydroxide are completely dissolved, reacting for 1h at 15 ℃ in a nitrogen atmosphere, centrifuging, washing and drying after the reaction is finished, so as to obtain benzotriazole-based polyethylene glycol modified montmorillonite;

(7) adding a dichloromethane solvent, PET and benzotriazole-based polyethylene glycol modified montmorillonite with the mass ratio of 100:1 into a reactor, stirring until uniform spinning solution is formed, pouring the spinning solution into a high-speed spinning machine for spinning, transferring the spinning solution to a drawing machine for drawing, and obtaining the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber.

And testing the tensile strength and the elongation at break of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber by using a BLD-1028A tensile strength testing machine and the tensile strength and the elongation at break of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber after being irradiated by ultraviolet rays for 60 hours.

And testing the impact strength of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber and the impact strength of the organic montmorillonite toughened and modified PET anti-ultraviolet aging fiber after being irradiated by ultraviolet rays for 60 hours by using an HH300-500J impact strength tester.