Outdoor high-strength waterproof polyester fiber and preparation method thereof

Abstract

The invention discloses an outdoor high-strength waterproof polyester fiber and a preparation method thereof, belongs to the technical field of polyester fibers, and is used for solving the technical problem that the mechanical property and waterproof capacity of the outdoor polyester fiber in the prior art do not reach the standard. The preparation method comprises the following steps: adding modified polyester master batches into a screw extruder for melt extrusion, spinning and stretching to obtain filaments; cooling and curing the filaments, and synthesizing modified polyester fibers; adding the modified polyester fiber into the water-repellent finishing liquid for post-finishing to obtain the finished polyester fiber; and drying and baking the finished polyester fiber to obtain the outdoor high-strength waterproof polyester fiber. In the process of synthesizing the polyester master batch, a composite elastomer obtained by addition of gutta-percha and rosin is added for toughening, so that the mechanical property of the synthesized modified polyester is improved. The water-repellent finishing liquid is prepared by reacting cochineal, metal ions and hydrolyzed trichlorosilane. The polyester fiber prepared by the invention has the characteristics of good mechanical property and high waterproofness.

Description

Technical Field

[0001] The present invention relates to the technical field of polyester fibers, and in particular to a high-strength waterproof polyester fiber for outdoor use and a preparation method thereof. Background Art

[0002] Polyester is a fiber-forming polymer made from dimethyl 1,4-phthalate and ethylene glycol through esterification or transesterification and polycondensation reactions; polyester fiber is also the most widely used and most widely consumed synthetic fiber. The ester group and benzene ring of polyester form a rigid conjugated system, restricting the free rotation of the flexible aliphatic hydrocarbon group. Therefore, compared with other fibers, polyester fiber has the advantages of a higher melting point, greater rigidity, and higher strength. However, the strength of ordinary polyester still cannot meet the industrial demand for high-strength products such as curtain fabrics, outdoor canvas, and military fabrics. In addition, due to the high geometric regularity and high crystallinity of the polyester molecular structure, it is difficult to modify, which limits the improvement of its waterproof function and makes it difficult to use as an outdoor fabric.

[0003] Patent application CN103088460A discloses a high-strength industrial polyester fiber and its preparation method. The polyester fiber comprises a PET matrix and Ti dispersed in the PET matrix. x (OR 1 O) y (OOCC6H4COO) z H4. By introducing lamellar nanomaterials into the PET matrix, the mechanical properties are improved by inducing orientation of the PET molecular chains during processing. However, the synthetic polyester fibers are highly chemically inert and cannot be modified with water-repellent materials. This results in a lack of water-repellency and poor suitability for outdoor use.

[0004] In view of the technical defects in this aspect, a solution is now proposed. Summary of the Invention

[0005] The purpose of the present invention is to provide a high-strength waterproof polyester fiber for outdoor use and a preparation method thereof, so as to solve the technical problems of poor mechanical properties and poor waterproof ability of outdoor polyester fibers in the prior art.

[0006] The purpose of the present invention can be achieved by the following technical solution: A method for preparing high-strength waterproof polyester fiber for outdoor use, comprising the following steps:

[0007] S1. The modified polyester masterbatch is vacuum dried and added to a screw extruder for melt extrusion at a screw box temperature of 265-275°C, and then spun and stretched to obtain filaments; the filaments are cooled and solidified to synthesize modified polyester fibers;

[0008] S2. The modified polyester fiber is added to a water-repellent finishing liquid for post-finishing at a bath ratio of 1:25-30 to obtain a finished polyester fiber; the finished polyester fiber is dried and baked to obtain a high-strength waterproof polyester fiber for outdoor use.

[0009] Furthermore, in step S1, the method for preparing the modified polyester masterbatch comprises the following steps:

[0010] A1. Dissolve eucommia gum in toluene, then add rosin and an initiator to obtain a mixture; react the mixture at 75-85° C. for 4-6 hours to obtain a product; and perform post-processing on the product to prepare a composite elastomer;

[0011] A2, dimethyl 1,4-phthalate, ethylene glycol, and a catalyst are added to the transesterification kettle, which is heated to 190-195°C and reacted at this temperature for 2-3 hours. The transesterification rate is determined to be 80-85% based on the amount of distilled methanol, which indicates the completion of the first reaction stage. The composite elastomer is then added to the transesterification kettle, and esterification is continued at a constant temperature for 1-2 hours, which indicates the completion of the second reaction stage to obtain an intermediate.

[0012] A3. Add a stabilizer to the intermediate and distill off excess ethylene glycol to obtain a reacted material; the reacted material is subjected to post-processing to prepare a modified polyester masterbatch.

[0013] The present invention utilizes an intermittent transesterification polycondensation process to prepare a modified polyester masterbatch. The polycondensation process can be divided into a first stage and a second stage. In the first stage, dimethyl 1,4-phthalate and ethylene glycol undergo an ester exchange reaction to produce an intermediate and release methanol; the ethylene glycol is slightly in excess. In the second stage, the carboxyl groups of the composite elastomer continue to react with the alcoholic hydroxyl groups of the intermediate to produce a modified polyester masterbatch modified with the composite elastomer.

[0014] Furthermore, in step A1, the initiator is dibenzoyl peroxide; the usage ratio of eucommia gum, toluene, rosin and initiator is 5-10g:200-400mL:5-12g:0.5-1g; the post-processing step includes: placing the product in anhydrous ethanol for precipitation to obtain a precipitate; washing the precipitate with ethanol, and then drying to remove the toluene solvent to obtain a composite elastomer.

[0015] Furthermore, in step A2, the catalyst is tetrabutyl titanate, the amount ratio of dimethyl 1,4-phthalate, ethylene glycol and composite elastomer is 19.4-38.8g:12-24g:10-25g, and the amount of catalyst is 50-80ppm of dimethyl 1,4-phthalate; in step A3, the stabilizer is trimethyl phosphate, the amount of intermediate is 35-75g, and the amount of stabilizer is 40-100ppm of dimethyl 1,4-phthalate; the post-processing steps include: transferring the reacted material to a polycondensation kettle with nitrogen, and conducting a polycondensation reaction under vacuum; after the polycondensation reaction is completed, obtaining a product; using nitrogen to extrude all the product, casting and pelletizing, to obtain a modified polyester masterbatch.

[0016] Furthermore, in step S1, the vacuum drying temperature is 115-135° C., the vacuum drying time is 3-4 hours, the spinning speed is 1000-1500 m / min, and the stretching ratio is 2-4 times.

[0017] Furthermore, in step S2, the preparation method of the water-repellent finishing liquid comprises the following steps:

[0018] B1. Add dye powder to NaOH solution and stir at 60-70°C until the dye powder is completely dissolved to obtain a powder solution;

[0019] B2. Deionized water, copper chloride, and zinc chloride are sequentially added to the powder solution to obtain a dye powder solution; wherein the concentration of the dye powder is 10-15 g / L, the concentration of the copper chloride is 1-5 g / L, and the concentration of the zinc chloride is 1-5 g / L, and the dye powder solution is then subjected to high-speed shear emulsification to obtain an organically coordinated metal ion solution;

[0020] B3. Preheat trichlorosilane to 150-200°C to obtain preheated gas; heat the reactor to 200-220°C, and pass the preheated gas into the reactor until the reactor is filled with trichlorosilane gas; then spray the organically coordinated metal ion solution into the reactor, carry out constant temperature circulation reaction for 2-3 hours, and then cool to room temperature. Collect the liquid to obtain the prepared water-repellent finishing liquid.

[0021] Furthermore, in step B1, the concentration of the NaOH solution is 0.1 mol / L, the high-speed shearing speed is 1000-2000 r / min, and the emulsification time is 20-30 min; in step B2, the reactor volume is 500 mL, and the amount of the organically coordinated metal ion solution is 30-50 mL.

[0022] Furthermore, in step S2, the post-finishing adopts a two-immersion and two-rolling process with a rolling rate of 90-95%; the drying temperature is 90-100°C and the drying time is 10-15 minutes; the baking temperature is 110-120°C and the baking time is 3-5 minutes.

[0023] As another aspect of the present invention, a method for preparing high-strength waterproof polyester fiber for outdoor use is provided to prepare high-strength waterproof polyester fiber for outdoor use.

[0024] The present invention has the following beneficial effects:

[0025] 1. This invention uses dimethyl 1,4-phthalate and ethylene glycol as monomers to synthesize a polyester masterbatch. An appropriate amount of composite elastomer is added during toughening modification. The composite elastomer is an addition product of eucommia gum and rosin. The main component of natural eucommia gum is trans-1,4-polyisoprene; the chemical components of rosin are primarily abietic acid, neoabietic acid, l-alginic acid, and palustric acid, containing various functional groups such as conjugated double bonds and carboxyl groups. In the presence of an initiator and using toluene as a solvent, eucommia gum and rosin undergo a double bond addition reaction to synthesize the composite elastomer. By adding an appropriate amount of elastomer during the polyester masterbatch synthesis process, the toughness of the resulting polyester masterbatch can be significantly improved. Furthermore, both rosin and natural eucommia gum are non-toxic to humans and organisms, making them exemplary environmentally friendly materials.

[0026] 2. Cochineal carmine, an anthraquinone-based natural dye, contains polyhydroxy and polycarboxyl functional groups, capable of forming salts with polyvalent metal ions, thereby synthesizing organically coordinated metal ions with copper and zinc ions. When trichlorosilane is introduced into a solution of organically coordinated metal ions, it undergoes further hydrolysis under high temperature and thermal cycling conditions, chelating the metal ions and producing a water-repellent finish containing polysilicon, polymetallic ions, and polyhydroxycarboxyl groups. This water-repellent finish is then applied to the modified polyester fiber for post-finishing. The carboxyl functional groups of the composite elastomer in the modified polyester fiber react with the polyol hydroxyl functional groups in the water-repellent finish, thereby enhancing the fastness of the finish in the modified polyester fiber and improving its water resistance and mechanical properties. After a double drying process, a high-strength, waterproof polyester fiber for outdoor use is produced. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0028] Figure 1This is a process flow chart for preparing high-strength waterproof polyester fiber for outdoor use according to the present invention. DETAILED DESCRIPTION

[0029] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0030] The eucommia gum used in Examples 1-3 of the present invention was purchased from Shaanxi Jingfei Biotechnology Co., Ltd., with model number 9003-31-0, an average molecular weight of 160,000-170,000, and a Mooney viscosity of 40-60; the rosin used in Examples 1-3 of the present invention was purchased from Anhui Kangwei Fuqi Pharmaceutical Co., Ltd.; the cochineal carmine used in Examples 4-6 of the present invention was purchased from Jiangsu Shunying Biotechnology Co., Ltd., with CAS number 1390-65-4.

[0031] Example 1

[0032] This embodiment provides a method for preparing a modified polyester masterbatch for outdoor high-strength waterproof polyester fiber, comprising the following steps:

[0033] A1, 5 g of Eucommia gum, and 200 mL of toluene were added to a 250 mL beaker and dissolved with stirring at 75°C for 6 h. Then, 5 g of rosin and 0.5 g of dibenzoyl peroxide (initiator) were added to the beaker to obtain a mixture. The beaker was kept at a constant temperature, and the reaction continued at this temperature for 4 h to obtain the product. The product was precipitated in anhydrous ethanol to obtain a precipitate. The precipitate was washed with ethanol and dried in a forced air oven to constant weight to remove the toluene solvent, thereby obtaining a composite elastomer.

[0034] A2, 19.4 g of dimethyl 1,4-phthalate, 12 g of ethylene glycol and catalyst tetrabutyl titanate (the amount of catalyst used is 50 ppm of dimethyl 1,4-phthalate) were added to a 1000 mL laboratory transesterification kettle. The transesterification kettle was heated to 190° C. and reacted at this temperature for 2 hours. The methanol generated by the reaction was distilled and recovered through a fractionating tower. Based on the amount of distilled methanol, the transesterification rate was determined to be 80%, which was considered to be the end of the first reaction stage. Then, 10 g of the composite elastomer was added to the transesterification kettle, and the esterification reaction was continued at a constant temperature for 1 hour. The second reaction stage was considered to be the end to obtain an intermediate.

[0035] A3. Retain 35g of the intermediate in the transesterification reactor. Then, add trimethyl phosphate (40 ppm of dimethyl 1,4-phthalate) as a stabilizer and distill off excess ethanol to obtain the reacted material. Transfer the reacted material from the transesterification reactor via a filter to a polycondensation reactor using nitrogen. Polycondensation is carried out under vacuum at a pressure of -100 Pa for 2 hours at a temperature of 255°C. After completion of the polycondensation reaction, a product is obtained. The product is extruded with nitrogen and pelletized from the casting strip to obtain a modified polyester masterbatch.

[0036] Example 2

[0037] This embodiment provides a method for preparing a modified polyester masterbatch for outdoor high-strength waterproof polyester fiber, comprising the following steps:

[0038] A1. Add 8 g of Eucommia gum and 300 mL of toluene to a 250 mL beaker and stir to dissolve at 80°C for 7 hours. Then, add 8 g of rosin and 0.8 g of dibenzoyl peroxide (initiator) to the beaker to obtain a mixture. Maintain the beaker at a constant temperature and continue the reaction at this temperature for 5 hours to obtain the product. The product is precipitated in anhydrous ethanol to obtain a precipitate. The precipitate is washed with ethanol and then dried in a forced air oven to constant weight to remove the toluene solvent, thereby obtaining a composite elastomer.

[0039] A2. 29 g of dimethyl 1,4-phthalate, 18 g of ethylene glycol, and a catalyst, tetrabutyl titanate (the amount of the catalyst used is 60 ppm of dimethyl 1,4-phthalate) were added to a 1000 mL laboratory transesterification kettle. The temperature of the transesterification kettle was raised to 192° C. and the reaction was carried out at this temperature for 2.5 hours. The methanol generated by the reaction was distilled and recovered through a fractionating tower. Based on the amount of distilled methanol, the transesterification rate was determined to be 82%, and the first reaction stage was considered to be completed. 20 g of the composite elastomer was then added to the transesterification kettle, and the esterification reaction was continued at a constant temperature for 1.5 hours. The second reaction stage was considered to be completed to obtain an intermediate.

[0040] A3. Retain 65g of the intermediate in the transesterification reactor. Then, add trimethyl phosphate (70 ppm of dimethyl 1,4-phthalate) as a stabilizer and distill off excess ethanol to obtain the reacted material. Transfer the reacted material from the transesterification reactor via a filter to a polycondensation reactor using nitrogen. Polycondensation is carried out under vacuum at a pressure of -150 Pa for 2.6 hours at a temperature of 260°C. After completion of the polycondensation reaction, a product is obtained. The product is extruded with nitrogen and pelletized from a casting strip to obtain a modified polyester masterbatch.

[0041] Implementation 3

[0042] This embodiment provides a method for preparing a modified polyester masterbatch for outdoor high-strength waterproof polyester fiber, comprising the following steps:

[0043] A1. Add 10 g of Eucommia gum and 400 mL of toluene to a 250 mL beaker and dissolve with stirring at 85°C for 8 hours. Then, add 12 g of rosin and 1 g of dibenzoyl peroxide (initiator) to the beaker to obtain a mixture. Maintain the beaker at a constant temperature and continue the reaction at this temperature for 6 hours to obtain the product. The product is precipitated in anhydrous ethanol to obtain a precipitate. The precipitate is washed with ethanol and then dried in a forced air oven to constant weight to remove the toluene solvent, thereby obtaining a composite elastomer.

[0044] A2. 38.8 g of dimethyl 1,4-phthalate, 24 g of ethylene glycol, and a catalyst, tetrabutyl titanate (the amount of the catalyst is 80 ppm of dimethyl 1,4-phthalate) were added to a 1000 mL laboratory transesterification kettle. The transesterification kettle was heated to 195° C. and reacted at this temperature for 3 h. The methanol generated by the reaction was distilled and recovered through a fractionating tower. Based on the amount of distilled methanol, the transesterification rate was determined to be 85%, indicating the completion of the first reaction stage. 25 g of the composite elastomer was then added to the transesterification kettle, and the esterification reaction was continued at a constant temperature for 2 h. This was considered the completion of the second reaction stage to obtain an intermediate.

[0045] A3. Retain 75g of the intermediate in the transesterification kettle. Then, add 100ppm of trimethyl phosphate (stabilizer: 100ppm based on dimethyl 1,4-phthalate) and distill off excess ethanol to obtain the reacted material. Transfer the reacted material from the transesterification kettle via a filter to a polycondensation kettle using nitrogen. Polycondensation is carried out under vacuum at a pressure of -200 Pa, a duration of 3 hours, and a temperature of 265°C. After completion of the polycondensation reaction, a product is obtained. The product is extruded with nitrogen and pelletized into a cast strip to obtain a modified polyester masterbatch.

[0046] Example 4

[0047] This embodiment provides a method for preparing a water-repellent finishing liquid for outdoor high-strength waterproof polyester fibers, comprising the following steps:

[0048] B1. Measure 30 mL of 0.1 mol / L NaOH solution and add it to a 250 mL beaker. Then weigh 3 g of cochineal dye powder and add it to the beaker. Then use a magnetic heating stirrer to stir at 60°C until the dye powder is completely dissolved to obtain a powder solution.

[0049] B2. Deionized water, copper chloride, and zinc chloride were sequentially added to the beaker to obtain a dye powder solution; wherein the concentration of the dye powder was 10 g / L, the concentration of the copper chloride was 1 g / L, and the concentration of the zinc chloride was 1 g / L; the dye powder solution was emulsified using a high-speed shear emulsifier at 1000 r / min for 20 min to obtain an organically coordinated metal ion solution.

[0050] B3. Select a 500mL stainless steel reactor containing nickel and chromium. Install an upward-facing nozzle at the bottom of the reactor. Preheat trichlorosilane to 150°C to obtain preheated gas. Heat the reactor to 200°C and introduce the preheated gas into the reactor at a rate of 10mL / min until the reactor is filled with trichlorosilane gas. Spray 30mL of an organically coordinated metal ion solution into the reactor through the nozzle. Circulate the reaction within the reactor for 2 hours, then cool to room temperature to obtain a water-repellent finishing solution.

[0051] Example 5

[0052] This embodiment provides a method for preparing a water-repellent finishing liquid for outdoor high-strength waterproof polyester fibers, comprising the following steps:

[0053] B1. Measure 35 mL of 0.1 mol / L NaOH solution and add it to a 250 mL beaker. Then weigh 4 g of cochineal dye powder and add it to the beaker. Then use a magnetic heating stirrer to stir at 65°C until the dye powder is completely dissolved to obtain a dye powder solution.

[0054] B2. Deionized water, copper chloride, and zinc chloride were sequentially added to the beaker to obtain a dye powder solution; wherein the concentration of the dye powder was 12 g / L, the concentration of the copper chloride was 3 g / L, and the concentration of the zinc chloride was 3 g / L; the dye powder solution was emulsified using a high-speed shear emulsifier at 1500 r / min for 25 min to obtain an organically coordinated metal ion solution.

[0055] B3. Select a 500mL stainless steel reactor containing nickel and chromium. Install an upward-facing nozzle at the bottom of the reactor. Preheat trichlorosilane to 180°C to obtain preheated gas. Heat the reactor to 210°C and introduce the preheated gas into the reactor at a rate of 10mL / min until the reactor is filled with trichlorosilane gas. Spray 40mL of an organically coordinated metal ion solution into the reactor through the nozzle. Circulate the reaction within the reactor for 2.5 hours, then cool to room temperature to obtain a water-repellent finishing solution.

[0056] Example 6

[0057] This embodiment provides a method for preparing a water-repellent finishing liquid for outdoor high-strength waterproof polyester fibers, comprising the following steps:

[0058] B1. Measure 40 mL of 0.1 mol / L NaOH solution and add it to a 250 mL beaker. Then weigh 5 g of cochineal dye powder and add it to the beaker. Then use a magnetic heating stirrer to stir at 70°C until the dye powder is completely dissolved to obtain a dye powder solution.

[0059] B2. Deionized water, copper chloride, and zinc chloride were sequentially added to the beaker to obtain a dye powder solution; wherein the concentration of the dye powder was 15 g / L, the concentration of the copper chloride was 5 g / L, and the concentration of the zinc chloride was 5 g / L; the dye powder solution was emulsified using a high-speed shear emulsifier at 2000 r / min for 30 min to obtain an organically coordinated metal ion solution.

[0060] B3. Select a 500mL stainless steel reactor containing nickel and chromium. Install an upward-facing nozzle at the bottom of the reactor. Preheat trichlorosilane to 200°C to obtain preheated gas. Heat the reactor to 220°C and introduce the preheated gas into the reactor at a rate of 10mL / min until the reactor is filled with trichlorosilane gas. Spray 50mL of an organically coordinated metal ion solution into the reactor through the nozzle. Circulate the reaction within the reactor for 3 hours, then cool to room temperature to obtain a water-repellent finishing solution.

[0061] Example 7

[0062] This embodiment provides a method for preparing high-strength waterproof polyester fiber for outdoor use, comprising the following steps:

[0063] S1. The modified polyester masterbatch prepared in Example 1 was dried in a vacuum drum dryer at a drying temperature of 115°C for 3 hours to obtain dried masterbatch. The dried masterbatch was added to a screw extruder for melt extrusion at a screw box temperature of 265°C, a spinning speed of 1000 m / min, and a post-stretching ratio of 2 to obtain filaments. The filaments were cooled and solidified to synthesize modified polyester fibers.

[0064] S2. The modified polyester fiber was immersed in the water-repellent finishing liquid prepared in Example 4 at a bath ratio of 1:25, an immersion temperature of 60° C., and an immersion time of 30 min to obtain the finished polyester fiber; the finished polyester fiber was dried at 90° C. for 10 min, and then baked in a baking machine at a baking temperature of 110° C. for 3 min to obtain a high-strength waterproof polyester fiber for outdoor use.

[0065] Example 8

[0066] This embodiment provides a method for preparing high-strength waterproof polyester fiber for outdoor use, comprising the following steps:

[0067] S1. The modified polyester masterbatch prepared in Example 2 was dried in a vacuum drum dryer at a drying temperature of 125°C for 3.5 hours to obtain dried masterbatch. The dried masterbatch was added to a screw extruder for melt extrusion at a screw box temperature of 270°C, a spinning speed of 1200 m / min, and a post-stretching ratio of 3 to obtain filaments. The filaments were cooled and solidified to synthesize modified polyester fibers.

[0068] S2. The modified polyester fiber was immersed in the water-repellent finishing liquid prepared in Example 5 at a bath ratio of 1:28, an immersion temperature of 65° C., and an immersion time of 50 min to obtain the finished polyester fiber; the finished polyester fiber was dried at 95° C. for 12 min, and then baked in a baking machine at a baking temperature of 115° C. for 4 min to obtain a high-strength waterproof polyester fiber for outdoor use.

[0069] Example 9

[0070] This embodiment provides a method for preparing high-strength waterproof polyester fiber for outdoor use, comprising the following steps:

[0071] S1. The modified polyester masterbatch prepared in Example 3 was dried in a vacuum drum dryer at a drying temperature of 135°C for 4 hours to obtain dried masterbatch. The dried masterbatch was added to a screw extruder for melt extrusion at a screw box temperature of 275°C, a spinning speed of 1500 m / min, and a post-stretching ratio of 4 to obtain filaments. The filaments were cooled and solidified to synthesize modified polyester fibers.

[0072] S2. The modified polyester fiber was immersed in the water-repellent finishing liquid prepared in Example 6 at a bath ratio of 1:30, an immersion temperature of 70° C., and an immersion time of 60 min to obtain the finished polyester fiber; the finished polyester fiber was dried at 100° C. for 15 min, and then baked in a baking machine at a baking temperature of 120° C. for 5 min to obtain a high-strength waterproof polyester fiber for outdoor use.

[0073] Comparative Example 1

[0074] The difference between this comparative example and Example 3 is that, when preparing the modified polyester masterbatch, step A1 is omitted; in step A2, during the second reaction stage, an equal mass of a mixture of eucommia gum and rosin is added to the transesterification kettle to replace the composite elastomer.

[0075] Comparative Example 2

[0076] The difference between this comparative example and Example 9 is that, when preparing the water-repellent finishing liquid, step B3 is omitted, and an organically coordinated metal ion solution is used as the water-repellent finishing liquid.

[0077] Comparative Example 3

[0078] The difference between this comparative example and Example 9 is that, when preparing the water-repellent finishing liquid, in step B2, no copper chloride and zinc chloride were added.

[0079] Performance testing:

[0080] 1. The modified polyester masterbatches prepared in Examples 1-3 and Comparative Example 1 were processed into dumbbell-shaped specimens, and the mechanical properties of the modified polyester masterbatches prepared in Examples 1-3 and Comparative Example 1 were tested in sequence using a universal tensile testing machine, with a tensile rate of 50 mm / min.

[0081] Table 1. Sample performance test data

[0082]

[0083] Performance Testing: Analysis of the data in Table 1 shows that the modified polyester masterbatches prepared in Examples 1-3 of the present invention exhibit excellent mechanical properties, as demonstrated by high values ​​for breaking strength and elongation at break. However, in Comparative Example 1, a mixture of eucommia gum and rosin was used in place of the composite elastomer to synthesize the modified polyester. Eucommia gum itself does not chemically react with polyester. Compared to the composite elastomer, the eucommia gum / rosin mixture exhibits lower compatibility and chemical fastness with the polyester masterbatch, as evidenced by lower values ​​for breaking strength and elongation at break.

[0084] The outdoor high-strength waterproof polyester fibers prepared in Examples 7-9 and Comparative Examples 1-3 were used as warp and weft yarns, with a density of 50 yarns / cm, to weave high-strength polyester fabrics, which were labeled as Examples 10-12 and Comparative Examples 4-6, respectively.

[0085] 2. The high-strength polyester fabrics prepared in Examples 10-12 and Comparative Examples 4-6 were cut into 1 cm × 2 cm specimens and fixed on a glass slide for testing. Water was ejected from a needle and dropped onto the fabric. Each fabric sample was tested three times to obtain the average water contact angle.

[0086] 3. Sequentially immerse the high-strength polyester fabrics prepared in Examples 10-12 and Comparative Examples 4-6 in 2 g / L soap solution, with a bath ratio of 1:50, at 40°C, and wash with shaking water for 10 min, followed by washing with clean water for 2 min. The above soaping is completed once, and repeated 5 times. The fabric is dried and the water repellency is measured. The water repellency grade is used to indicate the durability of the water repellent.

[0087] 4. In accordance with GB / T3923.1-2013 "Tensile Properties of Textile Fabrics," the high-strength polyester fabrics prepared in Examples 10-12 and Comparative Examples 4-6 were subjected to tensile strength tests using a YG026MB-250 electronic tensile testing machine. The tensile speed was 100 mm / min, the sample spacing was 200 nm, and each sample was tested five times to obtain the average value. The specific test results are shown in the table below:

[0088] Table 2. Sample performance test data

[0089]

[0090] Data Analysis: A comparative analysis of the data in the above table shows that the high-strength waterproof outdoor polyester fibers (Examples 10-12) prepared using the high-strength waterproof outdoor polyester fibers (Examples 7-9) of the present invention exhibit excellent water repellency, as evidenced by large water contact angles and high water repellency ratings. However, in Comparative Example 5 (using the water-repellent finishing solution prepared in Comparative Example 2), the organically coordinated metal ion solution did not further chelate with the trichlorosilane hydrolyzate to form an organosilicon polymer, thereby reducing the water repellency of the prepared high-strength waterproof outdoor polyester fibers, as evidenced by a lower water contact angle and a decreased water repellency rating.

[0091] When preparing a water-repellent finish, chelated metal ions act as a "mediator" to connect the cochineal carmine and trichlorosilane hydrolyzate in the finish. In Comparative Example 6 (using the water-repellent finish prepared in Comparative Example 3), copper chloride and zinc chloride were omitted. This resulted in the dispersion of the components of the finished finish, resulting in poor water repellency, poor washability, and a low water repellency rating.

[0092] Compared to the eucommia gum and rosin mixture, the composite elastomer itself significantly improves the mechanical properties of the polyester fiber produced. In Comparative Example 4 (using the water-repellent finishing liquid prepared in Comparative Example 1), replacing the composite elastomer with an equal mass of eucommia gum and rosin mixture resulted in a decrease in the mechanical properties of the high-strength polyester fabric produced in Comparative Example 4.

[0093] The above contents are merely examples and explanations of the structure of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they shall fall within the scope of protection of the present invention.

[0094] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0095] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing high-strength waterproof polyester fiber for outdoor use, characterized in that: The following steps are involved: S1. The modified polyester masterbatch is vacuum dried, added into a screw extruder for melt extrusion, the screw box temperature is 265-275°C, and spun and stretched to obtain filaments; The filaments are cooled and solidified to synthesize modified polyester fibers; S2. The modified polyester fiber is added to a water-repellent finishing liquid for post-finishing at a bath ratio of 1:25-30 to obtain a finished polyester fiber; the finished polyester fiber is dried and baked to obtain a high-strength waterproof polyester fiber for outdoor use.

2. The method for preparing a high-strength waterproof polyester fiber for outdoor use according to claim 1, characterized in that: In step S1, the method for preparing the modified polyester masterbatch comprises the following steps: A1. Dissolve eucommia gum in toluene, then add rosin and an initiator to obtain a mixture; react the mixture at 75-85° C. for 4-6 hours to obtain a product; and perform post-processing on the product to prepare a composite elastomer; A2, dimethyl 1,4-phthalate, ethylene glycol, and a catalyst are added to the transesterification kettle, which is heated to 190-195°C and reacted at this temperature for 2-3 hours. The transesterification rate is determined to be 80-85% based on the amount of distilled methanol, which indicates the completion of the first reaction stage. The composite elastomer is then added to the transesterification kettle, and esterification is continued at a constant temperature for 1-2 hours, which indicates the completion of the second reaction stage to obtain an intermediate. A3. Add a stabilizer to the intermediate and distill off excess ethylene glycol to obtain a reacted material; the reacted material is subjected to post-processing to prepare a modified polyester masterbatch.

3. The method for preparing a high-strength waterproof polyester fiber for outdoor use according to claim 2, characterized in that: In step A1, the initiator is dibenzoyl peroxide; the usage ratio of eucommia gum, toluene, rosin and initiator is 5-10g:200-400mL:5-12g:0.5-1g; the post-processing step includes: placing the product in anhydrous ethanol for precipitation to obtain a precipitate; washing the precipitate with ethanol, and then drying to remove the toluene solvent to obtain a composite elastomer.

4. The method for preparing a high-strength waterproof polyester fiber for outdoor use according to claim 2, characterized in that: In step A2, the catalyst is tetrabutyl titanate, the amount ratio of dimethyl 1,4-phthalate, ethylene glycol and composite elastomer is 19.4-38.8g:12-24g:10-25g, and the amount of catalyst is 50-80ppm of dimethyl 1,4-phthalate; in step A3, the stabilizer is trimethyl phosphate, the amount of intermediate is 35-75g, and the amount of stabilizer is 40-100ppm of dimethyl 1,4-phthalate; the post-processing steps include: transferring the reacted material to a polycondensation kettle with nitrogen, carrying out a polycondensation reaction under vacuum, the vacuum pressure is -100~-200Pa, the polycondensation time is 2-3h, and the polycondensation temperature is 255-265°C; after the polycondensation reaction is completed, a product is obtained; the product is completely extruded with nitrogen, and pelletized into a cast strip to obtain a modified polyester masterbatch.

5. The method for preparing a high-strength waterproof polyester fiber for outdoor use according to claim 1, characterized in that: In step S1, the vacuum drying temperature is 115-135° C., the vacuum drying time is 3-4 hours, the spinning speed is 1000-1500 m / min, and the stretching ratio is 2-4 times.

6. The method for preparing a high-strength waterproof polyester fiber for outdoor use according to claim 1, characterized in that: In step S2, the method for preparing the water-repellent finishing liquid comprises the following steps: B1. Add dye powder to NaOH solution and stir at 60-70°C until the dye powder is completely dissolved to obtain a powder solution; B2. Deionized water, copper chloride, and zinc chloride are sequentially added to the powder solution to obtain a dye powder solution; wherein the concentration of the dye powder is 10-15 g / L, the concentration of the copper chloride is 1-5 g / L, and the concentration of the zinc chloride is 1-5 g / L, and the dye powder solution is then subjected to high-speed shear emulsification to obtain an organically coordinated metal ion solution; B3. Preheat trichlorosilane to 150-200°C to obtain preheated gas; heat the reactor to 200-220°C, and pass the preheated gas into the reactor until the reactor is filled with trichlorosilane gas; then spray the organically coordinated metal ion solution into the reactor, carry out constant temperature circulation reaction for 2-3 hours, and then cool to room temperature. Collect the liquid to obtain the prepared water-repellent finishing liquid.

7. The method for preparing high-strength waterproof polyester fiber for outdoor use according to claim 6, characterized in that: In step B1, the concentration of the NaOH solution is 0.1 mol / L, the high-speed shearing speed is 1000-2000 r / min, and the emulsification time is 20-30 min; in step B2, the reactor volume is 500 mL, and the amount of the organically coordinated metal ion solution is 30-50 mL.

8. The method for preparing outdoor high-strength waterproof polyester fiber according to claim 1, characterized in that: In step S2, the post-finishing adopts a two-immersion and two-rolling process with a rolling rate of 90-95%; the drying temperature is 90-100° C. and the drying time is 10-15 minutes; the baking temperature is 110-120° C. and the baking time is 3-5 minutes.

9. A high-strength waterproof polyester fiber for outdoor use, characterized in that: The high-strength waterproof polyester fiber for outdoor use is prepared by the preparation method of any one of claims 1 to 8.

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