Titanium-based matting polyester fiber and preparation method thereof

Abstract

The invention relates to the field of fibers, and provides a titanium-based matting polyester fiber and a preparation method thereof, the polyester fiber comprises the following raw materials by weight: 90-110 parts of polyester, 1-3 parts of a titanium-based matting agent, 1-4 parts of a flame retardant, 0.5-2 parts of an antioxidant, and 2-6 parts of an oil agent. The titanium-based delustering polyester fiber provided by the invention has excellent delustering performance and also has good antibacterial property and mechanical property.

Description

Technical Field

[0001] The present invention relates to the field of fibers, and in particular to a titanium-based matte polyester fiber and a preparation method thereof. Background Art

[0002] Polyester fiber is a type of synthetic fiber, commonly known as polyester. It is a polymer compound usually made by the esterification reaction of terephthalic acid and ethylene glycol. Polyester fiber has the advantages of good elasticity, high strength and excellent wear resistance. It is widely used in clothing, home textiles, and decorations, becoming one of the most widely used fibers in the current textile industry.

[0003] With economic development, people are paying more and more attention to the visual effects of fabrics in polyester filament production. To achieve a cotton-like fabric effect and eliminate the bright luster of polyester, manufacturers may add a certain amount of matting agent, such as titanium dioxide, to the filaments to produce matting fibers, eliminating the aurora effect of the fabric. The addition of titanium dioxide can also improve the antibacterial and mechanical properties of polyester fibers. However, titanium dioxide is a granular material that easily agglomerates, and its surface is hydrophilic, making it less compatible with the polyester matrix. As a result, when used alone, it has a poor effect on improving the matting, antibacterial, and mechanical properties of polyester fibers.

[0004] Patent CN 111254504 B discloses a fully matte, lightweight, moisture-absorbing, quick-drying polyester fiber and a preparation method thereof, comprising the following steps: adding a screw extruder to a melt-spun semi-matt polyester fiber production line, adding matte polyester masterbatch thereto, and obtaining a matte polyester masterbatch melt by melt extrusion; injecting a matte polyester masterbatch melt containing a high concentration of titanium dioxide into the main melt before the melt is transported to a spinning manifold for spinning, thereby increasing the final titanium dioxide content in the polyester fiber and ensuring melt stability; and achieving a simple production process and low production cost. However, the problem of easy agglomeration of titanium dioxide materials is not solved, and certain application limitations still exist.

[0005] Therefore, there is an urgent need on the market for a titanium-based matte polyester fiber that has excellent matte properties while also having good antibacterial and mechanical properties. Summary of the Invention

[0006] In response to the problems existing in the prior art, the present invention uses polyester as the base material and designs to add a titanium-based matting agent. The titanium-based matting agent is composed of modified titanium dioxide, kaolin and barium sulfate. It is combined with a flame retardant, an antioxidant and an oil agent to synthesize a titanium-based matting polyester fiber. This solves the problems of poor dispersibility and compatibility of titanium dioxide in polyester, so that the polyester fiber has excellent matting properties while also having good antibacterial and mechanical properties.

[0007] In order to achieve the above object, the technical solution adopted by the present invention is as follows: On one hand, the present invention provides a titanium-based matting polyester fiber. The polyester fiber comprises the following raw materials, measured by weight: 90-110 parts of polyester, 1-3 parts of a titanium-based matting agent, 1-4 parts of a flame retardant, 0.5-2 parts of an antioxidant, and 2-6 parts of an oil agent.

[0008] In some embodiments of the present invention, the polyester is any one of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate.

[0009] In some embodiments of the present invention, the titanium-based matting agent is a mixture of modified titanium dioxide, kaolin and barium sulfate.

[0010] Preferably, the mass ratio of modified titanium dioxide, kaolin and barium sulfate in the titanium-based matting agent is 1: (0.4-0.6): (0.2-0.4).

[0011] More preferably, the mass ratio of modified titanium dioxide, kaolin and barium sulfate in the titanium-based matting agent is 1:0.5:0.25.

[0012] The applicant combines a small amount of kaolin and barium sulfate with low refractive index with modified titanium dioxide to form a titanium-based matting agent, which synergistically improves hiding power and dispersibility, and also reduces the amount of titanium dioxide used, reducing costs and the impact of its photocatalytic side effects on polyester fibers.

[0013] In some embodiments of the present invention, the method for preparing the modified titanium dioxide comprises the following steps: (1) Add titanium dioxide to deionized water, stir, add Tris-HCl and dopamine hydrochloride in sequence, stir, filter, wash, dry, grind, and obtain product 1 for later use; (2) Add 3-mercaptopropyltrimethoxysilane and ammonia water to an ethanol aqueous solution, react at 60-70°C for 2.5-3.5 hours, let it stand, add the product 1 of step (1) while stirring, stir under an inert atmosphere for 5-7 hours, centrifuge, wash, dry, grind, and obtain product 2 for use; (3) Add polyhexamethyleneguanidine phosphate to deionized water and stir to obtain a solution for use. Add the product 2 of step (2) to deionized water, add the solution and stir. Add tetramethylethylenediamine and react at 45-55°C for 5-7h. Centrifuge, wash and dry to obtain modified titanium dioxide.

[0014] Wherein, the titanium dioxide is nano titanium dioxide with an average particle size of 5-10 nm.

[0015] In some embodiments of the present invention, in step (2), the mass ratio of product 1 to 3-mercaptopropyltrimethoxysilane is 1:(0.4-0.6).

[0016] Preferably, in step (2), the mass ratio of product 1 to 3-mercaptopropyltrimethoxysilane is 1:0.45.

[0017] In some embodiments of the present invention, in step (3), the mass ratio of product 2 to polyhexamethyleneguanidine phosphate is 1:(2.5-3.5).

[0018] Preferably, in step (3), the mass ratio of product 2 to polyhexamethyleneguanidine phosphate is 1:3.

[0019] Titanium dioxide, especially nano-scale titanium dioxide, has a large difference in refractive index from the polyester matrix. A small amount of addition can produce strong scattering intensity, achieving an efficient extinction effect. Titanium dioxide also has good antibacterial and mechanical properties. However, nano-titanium dioxide is prone to agglomeration due to its small particle size and high surface energy, which in turn causes the extinction, antibacterial and mechanical properties of polyester fibers to fail to achieve the ideal effect.

[0020] In order to solve the above problems, the applicant first pre-coated titanium dioxide with polydopamine to reduce the surface energy of nano titanium dioxide, and then introduced 3-mercaptopropyltrimethoxysilane to modify it. The thiol group and the amino group on the surface of polydopamine were coupled, and a product 2 having a network structure and rich in thiol groups was formed without changing the crystal form of nano titanium dioxide, further improving the dispersibility of nano titanium dioxide; further, the applicant selected polyhexamethyleneguanidine phosphate to graft-modify product 2, introducing a large number of cationic groups, and significantly improving the dispersibility of modified titanium dioxide in polyester fibers through the dual effects of electrostatics and steric hindrance, thereby improving the overall mattness, antibacterial and mechanical properties of polyester fibers. The introduction of guanidine groups can improve the antibacterial properties of nano titanium dioxide, and the introduction of phosphate groups can make nano titanium dioxide more stable. In addition, there is an interaction between polyhexamethyleneguanidine phosphate and thiol groups, which can make the modified titanium dioxide more stable as a whole.

[0021] In some embodiments of the present invention, the flame retardant is triphenyl phosphate or ammonium polyphosphate.

[0022] In some embodiments of the present invention, the antioxidant is a hindered phenolic antioxidant.

[0023] Preferably, the hindered phenol antioxidant is antioxidant 1010.

[0024] In some embodiments of the present application, the oil agent is a mixture of fluorine-containing polyether and potassium phosphate ester.

[0025] Preferably, the mass ratio of fluorine-containing polyether and potassium phosphate ester in the oil agent is (5-7):1. In the present application, the potassium phosphate ester is potassium dodecyl phosphate or potassium isomeric tridecanol polyoxyethylene ether phosphate.

[0026] The fluorine-containing polyether can provide good smoothing, emulsifying and wetting functions, and can also provide a large number of hydrogen bonds for the oil agent system, improve the cloud point, and save energy; the potassium phosphate ester has good heat resistance and good antistatic property, and can enhance the antistatic effect of the fiber.

[0027] Another aspect of the present application also provides a preparation method of the titanium-based matt polyester fiber described in the above technical solution, which comprises the following steps: The polyester, titanium-based matting agent, flame retardant, antioxidant and oil agent are mixed, stirred at 110-130℃ for 20-40min, extruded, and melt spun to obtain the titanium-based matt polyester fiber.

[0028] Compared with the prior art, the present application has the following beneficial effects: (1) In the present application, polyester is used as the main material, and a titanium-based matting agent is designed to be added, which is composed of modified titanium dioxide, kaolin and barium sulfate, and is combined with a flame retardant, an antioxidant and an oil agent to synthesize a titanium-based matt polyester fiber. Through the synergistic effect of the components, the problem of poor dispersibility and compatibility of titanium dioxide in polyester is solved, so that the polyester fiber has excellent matt performance, good antibacterial property and mechanical property, and can be widely used in the field of fibers.

[0029] (2) In the present application, nano-titanium dioxide is modified by selecting polydopamine, 3-mercaptopropyl trimethoxysilane and polyhexamethylene guanidine phosphate, and the dispersibility of nano-titanium dioxide is improved, which has good dispersibility and compatibility in polyester, so that the modified titanium dioxide can play a better antibacterial property and mechanical property in the polyester fiber, and the modified titanium dioxide is combined with kaolin and barium sulfate to form a titanium-based matting agent, which improves the hiding power and dispersibility, and thus the polyester fiber has excellent matt property. DETAILED DESCRIPTION

[0030] The present application will be described below in conjunction with specific embodiments. It should be noted that the following examples are only used to illustrate the present application, and are not used to limit the present application. Other combinations and various modifications within the concept of the present application can be made without departing from the main idea or scope of the present application.

[0031] In the following examples and comparative examples, except for modified titanium dioxide, the remaining compound monomers and related reagents used can be purchased from the market, among which polyethylene terephthalate was purchased from Suzhou Chenzhituo Polymer Materials Co., Ltd.; polypropylene terephthalate was purchased from Dongguan Yingxiang Plastic Raw Materials Co., Ltd.; polybutylene terephthalate was purchased from Hubei Xinghengye Technology Co., Ltd.; titanium dioxide is nano titanium dioxide with an average particle size of 5 nm; the CAS number of polyhexamethylene guanidine phosphate is 89697-78-9; triphenyl phosphate was purchased from Shandong Polychemical Co., Ltd.; ammonium polyphosphate was purchased from Shandong Zhijia Chemical Technology Co., Ltd.; fluorinated polyether is polyether modified fluorosilicone oil, model TPD-8013, purchased from Fuzhou Taipuda New Materials Co., Ltd.; isomeric tridecyl alcohol polyoxyethylene ether phosphate potassium salt model E-1310PK, purchased from Green Union (Jining) Chemical Technology Co., Ltd.

[0032] Preparation Example 1 The synthesis method of modified titanium dioxide A comprises the following steps: (1) Add 15 g of titanium dioxide to 300 ml of deionized water and stir for 30 min. Then add 0.5 g of Tris-HCl and 0.15 g of dopamine hydrochloride in sequence and stir for 4 h. Filter and wash with deionized water. Dry at 120 °C for 5 h and grind to obtain product 1 for later use. (2) Add 4.5 g of 3-mercaptopropyltrimethoxysilane and 6 ml of 25 wt% ammonia water to 100 ml of 75 wt% ethanol aqueous solution, react at 65 ° C for 3 h, let it stand for 30 min, add 10 g of the product 1 of step (1) while stirring, stir for 6 h under nitrogen atmosphere, centrifuge, wash with deionized water and anhydrous ethanol three times, dry at 80 ° C for 10 h, grind, and obtain product 2 for use; (3) Add 15 g of polyhexamethyleneguanidine phosphate to 150 ml of deionized water and stir for 30 min to obtain a solution for use. Add 5 g of the product 2 of step (2) to 100 ml of deionized water, add the solution and stir. Add 0.1 g of tetramethylethylenediamine and react at 50 ° C for 6 h. Centrifuge, wash with deionized water, and dry to obtain modified titanium dioxide A.

[0033] Preparation Example 2 The specific implementation method of modified titanium dioxide B is the same as that of modified titanium dioxide A, except that the mass of 3-mercaptopropyltrimethoxysilane in step (2) is replaced with 3.5 g.

[0034] Preparation Example 3 The specific implementation method of modified titanium dioxide C is the same as that of modified titanium dioxide A, except that the mass of 3-mercaptopropyltrimethoxysilane in step (2) is replaced with 7 g.

[0035] Preparation Example 4 The specific implementation method of modified titanium dioxide D is the same as that of modified titanium dioxide A, except that the mass of polyhexamethyleneguanidine phosphate in step (3) is replaced with 12 g.

[0036] Preparation Example 5 The specific implementation method of modified titanium dioxide E is the same as that of modified titanium dioxide A, except that the mass of polyhexamethyleneguanidine phosphate in step (3) is replaced with 18.5 g.

[0037] Example 1 A titanium-based matting polyester fiber comprises the following raw materials, calculated by weight: 100 parts of polyethylene terephthalate, 2 parts of a titanium-based matting agent, 2.5 parts of triphenyl phosphate, 1 part of an antioxidant 1010, and 4 parts of an oiling agent.

[0038] The titanium-based matting agent is a mixture of modified titanium dioxide A, kaolin and barium sulfate, with a mass ratio of 1:0.5:0.25.

[0039] The oil agent is a mixture of fluorinated polyether and isomeric tridecanol polyoxyethylene ether phosphate potassium salt, with a mass ratio of 6:1.

[0040] The preparation method of titanium-based matte polyester fiber in this embodiment includes the following steps: Polyethylene terephthalate, titanium-based matting agent, triphenyl phosphate, antioxidant 1010 and oil are mixed, stirred at 120° C. for 30 minutes, extruded, and melt-spun at 280° C. to obtain titanium-based matting polyester fiber.

[0041] Example 2 A titanium-based matting polyester fiber comprises the following raw materials, calculated by weight: 90 parts of polytrimethylene terephthalate, 1 part of a titanium-based matting agent, 1 part of ammonium polyphosphate, 0.5 parts of an antioxidant 1010, and 2 parts of an oil agent.

[0042] The titanium-based matting agent is a mixture of modified titanium dioxide A, kaolin and barium sulfate, with a mass ratio of 1:0.4:0.2.

[0043] The oil agent is a mixture of fluorinated polyether and potassium lauryl phosphate with a mass ratio of 5:1.

[0044] The preparation method of titanium-based matte polyester fiber in this embodiment includes the following steps: Polypropylene terephthalate, titanium-based matting agent, ammonium polyphosphate, antioxidant 1010 and oil are mixed, stirred at 120° C. for 30 minutes, extruded, and melt-spun at 280° C. to obtain titanium-based matting polyester fiber.

[0045] Example 3 A titanium-based matting polyester fiber comprises the following raw materials, calculated by weight: 110 parts of polybutylene terephthalate, 3 parts of a titanium-based matting agent, 4 parts of triphenyl phosphate, 2 parts of an antioxidant 1010, and 6 parts of an oiling agent.

[0046] The titanium-based matting agent is a mixture of modified titanium dioxide A, kaolin and barium sulfate, with a mass ratio of 1:0.6:0.4.

[0047] The oil agent is a mixture of fluorinated polyether and isomeric tridecanol polyoxyethylene ether phosphate potassium salt, with a mass ratio of 7:1.

[0048] The preparation method of titanium-based matte polyester fiber in this embodiment includes the following steps: Polybutylene terephthalate, titanium-based matting agent, triphenyl phosphate, antioxidant 1010 and oil are mixed, stirred at 120° C. for 30 minutes, extruded, and melt-spun at 280° C. to obtain titanium-based matting polyester fiber.

[0049] Example 4 This embodiment provides a titanium-based matting polyester fiber and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the mass ratio of modified titanium dioxide A, kaolin and barium sulfate in the titanium-based matting agent is 1:0.8:0.6.

[0050] Example 5 This embodiment provides a titanium-based matte polyester fiber and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that the titanium-based matting agent is replaced by an equal amount of modified titanium dioxide A.

[0051] Example 6 This embodiment provides a titanium-based matte polyester fiber and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified titanium dioxide B replaces modified titanium dioxide A in equal amounts.

[0052] Example 7 This embodiment provides a titanium-based matte polyester fiber and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified titanium dioxide C replaces modified titanium dioxide A in equal amounts.

[0053] Example 8 This embodiment provides a titanium-based matte polyester fiber and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified titanium dioxide D replaces modified titanium dioxide A in equal amounts.

[0054] Example 9 This embodiment provides a titanium-based matte polyester fiber and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that modified titanium dioxide E replaces modified titanium dioxide A in equal amounts.

[0055] Example 10 This embodiment provides a titanium-based matte polyester fiber and a preparation method thereof. The specific implementation method is the same as that of Example 1, except that an equal amount of nano-titanium dioxide is used to replace the modified titanium dioxide A.

[0056] Performance Testing The matt properties, antibacterial properties and mechanical properties of the titanium-based matt polyester fibers of Examples 1-10 were tested, and the test results are shown in Table 1.

[0057] (1) Matting performance The sample uses barium sulfate as a reference, and the integrating sphere accessory is used to collect the sample's diffuse reflectance signal to visible light. The greater the diffuse reflectance, the better the extinction performance; (2) Antibacterial properties The antibacterial rate was tested and the antibacterial effect of titanium-based matte polyester fiber on Escherichia coli and Staphylococcus aureus was used as an example, referring to the national standard GB / T 20944.3-2008; (3) Mechanical properties The judgment is made by testing the breaking strength, referring to the standard GB / T 14344-2022 "Test method for tensile properties of chemical fiber filaments".

[0058] As can be seen from the data in Table 1, the titanium-based matting polyester fibers in Examples 1-3 of the present invention have good matting properties, antibacterial properties, and mechanical properties as a whole. In Example 4, the addition ratio of kaolin and barium sulfate in the titanium-based matting agent was changed, and in Example 5, kaolin and barium sulfate were not added to the titanium-based matting agent, which can produce certain photocatalytic side reactions, thereby reducing the matting properties of the polyester fiber to a certain extent. In Examples 6-9, the modification ratios of 3-mercaptopropyltrimethoxysilane and polyhexamethyleneguanidine phosphate to nano-titanium dioxide during the preparation of modified titanium dioxide were changed, respectively. Both resulted in a decrease in the dispersibility of the prepared modified titanium dioxide and poor improvement in antibacterial and mechanical properties, thereby reducing the overall matting, antibacterial, and mechanical properties of the polyester fiber. In Example 10, nano-titanium dioxide was used to replace modified titanium dioxide A in equal amounts. Testing found that the matting, antibacterial, and mechanical properties of the polyester fiber all showed worse results.

[0059] The above embodiments are only for illustrating the technical concept and features of the present invention. Its purpose is to enable people familiar with this technology to understand the content of the present invention and implement it. It cannot be used to limit the scope of protection of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A titanium-based matte polyester fiber, characterized in that: The polyester fiber comprises the following raw materials in parts by weight: 90-110 parts of polyester, 1-3 parts of titanium-based matting agent, 1-4 parts of flame retardant, 0.5-2 parts of antioxidant, and 2-6 parts of oil agent.

2. The titanium-based matte polyester fiber according to claim 1, characterized in that: The polyester is any one of polyethylene terephthalate, polypropylene terephthalate, and polybutylene terephthalate.

3. The titanium-based matte polyester fiber according to claim 1, characterized in that: The titanium-based matting agent is a mixture of modified titanium dioxide, kaolin and barium sulfate.

4. The titanium-based matte polyester fiber according to claim 1, characterized in that: The preparation method of the modified titanium dioxide comprises the following steps: (1) Add titanium dioxide to deionized water, stir, add Tris-HCl and dopamine hydrochloride in sequence, stir, filter, wash, dry, grind, and obtain product 1 for later use; (2) Add 3-mercaptopropyltrimethoxysilane and ammonia water to an ethanol aqueous solution, react at 60-70°C for 2.5-3.5 hours, let it stand, add the product 1 of step (1) while stirring, stir under an inert atmosphere for 5-7 hours, centrifuge, wash, dry, grind, and obtain product 2 for use; (3) Add polyhexamethyleneguanidine phosphate to deionized water and stir to obtain a solution for use. Add the product 2 of step (2) to deionized water, add the solution and stir. Add tetramethylethylenediamine and react at 45-55°C for 5-7h. Centrifuge, wash and dry to obtain modified titanium dioxide.

5. The titanium-based matte polyester fiber according to claim 4, characterized in that: In the step (2), the mass ratio of the product 1 to 3-mercaptopropyltrimethoxysilane is 1:(0.4-0.6).

6. The titanium-based matte polyester fiber according to claim 4, characterized in that: In the step (3), the mass ratio of the product 2 to the polyhexamethyleneguanidine phosphate is 1:(2.5-3.5).

7. The titanium-based matte polyester fiber according to claim 1, characterized in that: The flame retardant is triphenyl phosphate or ammonium polyphosphate.

8. The titanium-based matte polyester fiber according to claim 1, characterized in that: The antioxidant is a hindered phenol antioxidant.

9. The titanium-based matte polyester fiber according to claim 1, characterized in that: The oil agent is a mixture of fluorine-containing polyether and potassium phosphate.

10. A method for preparing the titanium-based matte polyester fiber according to any one of claims 1 to 9, characterized in that: The following steps are involved: The polyester, titanium-based matting agent, flame retardant, antioxidant and oil are mixed, stirred at 110-130° C. for 20-40 minutes, extruded, and melt-spun to obtain titanium-based matting polyester fiber.

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