Nano silver oxide modified polyester pre-oriented yarn and preparation method thereof

Abstract

The invention relates to the field of textile materials, and particularly discloses a nano silver oxide modified polyester pre-oriented yarn and a preparation method thereof. The nano silver oxide modified polyester pre-oriented yarn is prepared from the following raw materials in parts by weight: 90-110 parts of terephthalic acid, 40-60 parts of ethylene glycol, 0.5-0.8 part of nano silicon dioxide, 1-3 parts of a delustering agent and 1-3 parts of a dispersing agent, the matting agent comprises nano titanium dioxide, nano silver oxide is deposited on the surface of the nano titanium dioxide to form a nano silver oxide-titanium dioxide compound, and the surface of the nano silver oxide-titanium dioxide compound is subjected to wet modification through octadecylamine; according to the prepared nano silver oxide modified polyester pre-oriented yarn, wet modification is conducted through titanium dioxide, then wet modification is conducted through octadecylamine, antibacterial active ingredients can be stably and evenly dispersed in the polyester pre-oriented yarn raw materials, and the antibacterial durability of the polyester pre-oriented yarn is improved.

Description

Technical Field

[0001] The present application relates to the field of textile materials, and in particular to a nano silver oxide modified polyester pre-oriented yarn and a preparation method thereof. Background Art

[0002] Polyester pre-oriented yarn (POY) is an important synthetic fiber and is widely used in the textile industry. Due to its excellent physical properties and processing properties, polyester pre-oriented yarn is widely used in the production of various textiles, such as clothing, home textiles, industrial textiles, etc. With the development of science and technology, people have put forward higher requirements on the functionality and environmental protection of textile materials, especially the increasing demand for antibacterial and deodorizing properties. Therefore, the development of modified polyester pre-oriented yarn with special functions has become a research hotspot.

[0003] At present, in order to improve the antibacterial properties of polyester pre-oriented yarns, commonly used methods include surface coating treatment and the use of antibacterial finishing liquid. Surface coating treatment is to form a layer of antibacterial substance on the fiber surface through chemical plating, electroplating and other methods, which can easily cause the coating to fall off. The antibacterial finishing liquid has limited antibacterial treatment effect on polyester pre-oriented yarns. The antibacterial components cannot be firmly combined with polyester pre-oriented yarns, thereby reducing the durability of the antibacterial effect. Summary of the invention

[0004] In order to improve the durability of the antibacterial effect of polyester pre-oriented yarn, the present application provides a nano silver oxide modified polyester pre-oriented yarn and a preparation method thereof.

[0005] In the first aspect, the present application provides a nano-silver oxide modified polyester pre-oriented yarn, which adopts the following technical scheme: a nano-silver oxide modified polyester pre-oriented yarn, comprising the following raw materials in parts by weight: 90-110 parts of terephthalic acid, 40-60 parts of ethylene glycol, 0.5-1.5 parts of nano-silver oxide, 0.5-0.8 parts of nano-silicon dioxide, 0.1-0.3 parts of matting agent, and 1-3 parts of dispersant; the matting agent is nano-titanium dioxide, and nano-silver oxide is deposited on the surface of the nano-titanium dioxide to form a nano-silver oxide-titanium dioxide composite, and the surface of the nano-silver oxide-titanium dioxide composite is wet-modified with octadecylamine.

[0006] By adopting the above technical scheme, terephthalic acid and ethylene glycol react to generate polyester, and nano silver oxide is added during the polyester preparation reaction process, which can release silver ions in the polyester system to achieve antibacterial effect, and at the same time can also promote the prepared polyester pre-oriented yarn to have a more durable antibacterial durability. Nano silver oxide is deposited on the surface of nano titanium dioxide. Titanium dioxide, as a carrier of nano silver oxide, can not only promote the uniform dispersion of nano silver oxide, but also protect silver ions from being consumed prematurely, thereby prolonging the duration of the antibacterial activity of polyester pre-oriented yarn. In addition, titanium dioxide itself has photocatalytic activity, which can enhance the release of silver ions under light conditions, further improving the antibacterial effect and antibacterial durability of polyester pre-oriented yarn. Octadecanamine can be modified by wet method to evenly disperse nano silver oxide-titanium dioxide complex in polyester pre-oriented yarn raw materials, reduce the phenomenon of agglomeration of nano particles, and improve the uniform antibacterial effect of polyester pre-oriented yarn. At the same time, the long chain structure of octadecylamine can form a chemical bond with the surface of polyester pre-oriented yarn, improve the stability of antibacterial active ingredients in polyester pre-oriented yarn, prevent them from falling off during processing and use, and thus improve the durability of the antibacterial effect. The modification of octadecylamine can also improve the hydrophilicity of polyester pre-oriented yarn, so that polyester pre-oriented yarn can better absorb moisture, which helps release silver ions and further enhances the antibacterial effect and antibacterial durability.

[0007] Preferably, the polyester pre-oriented yarn raw material further comprises 5-10 parts of isophthalic acid and 1-3 parts of a silane coupling agent.

[0008] By adopting the above technical solution, isophthalic acid is added to the reaction process of terephthalic acid and ethylene glycol, which can destroy the integrity and order of polyester spherulites, reduce the crystallization rate and crystallinity of polyester, and thus improve the elongation at break and hygroscopicity of polyester pre-oriented yarns, which is beneficial to subsequent deformation and drafting. At the same time, in the isophthalic acid polyester system, it is beneficial to the diffusion and adsorption of water molecules, thereby improving the hygroscopicity of polyester pre-oriented yarns.

[0009] Silane coupling agent can form chemical bonds with nano silver oxide-titanium dioxide composite and the surface of polyester pre-oriented yarn, enhance the interfacial bonding between the two, prevent silver ions from falling off from the fiber surface during processing or use, and thus improve the durability of the antibacterial effect.

[0010] Preferably, the dispersant is sodium hexametaphosphate.

[0011] By adopting the above technical scheme, sodium hexametaphosphate is used as a dispersant, which can not only improve the dispersibility of the nano-silver oxide-titanium dioxide composite in the polyester pre-oriented yarn system, but also the lubricating effect of the dispersant can reduce the friction and static electricity accumulation generated by the polyester pre-oriented yarn during processing and use, thereby improving the antibacterial and antistatic effects of the polyester pre-oriented yarn.

[0012] Preferably, the particle size of the nano silver oxide is 10-25 nm, and the particle size of the titanium dioxide is 50-100 nm.

[0013] Preferably, the polyester pre-oriented yarn has a special-shaped cross-section, and the special-shaped cross-section is a cross-shaped cross-section.

[0014] By adopting the above technical solution, the polyester pre-oriented yarn with a cross-shaped cross-section has a larger specific surface area, and the grooves on the fiber surface have a wicking effect, which can improve the moisture absorption effect of the polyester pre-oriented yarn.

[0015] In a second aspect, the present application provides a method for preparing nano silver oxide modified polyester pre-oriented yarn, which adopts the following technical solution: A method for preparing nano silver oxide modified polyester pre-oriented yarn comprises the following specific steps: Depositing nano silver oxide on the surface of nano titanium dioxide by thermal deposition method to form a nano silver oxide-titanium dioxide composite, mixing the nano silver oxide-titanium dioxide composite with a dispersant, adding the composite to an octadecylamine solution, ultrasonically dispersing the composite, and drying the composite. Then, grinding the composite while adding a silane coupling agent to obtain a modified nano silver oxide-titanium dioxide composite; Terephthalic acid, ethylene glycol, modified nano silver oxide-titanium dioxide composite and nano silicon dioxide are mixed, heated and reacted to obtain a molten mixture, and the molten mixture is spun, cooled and stretched to obtain nano silver oxide modified polyester pre-oriented yarn.

[0016] By adopting the above technical scheme, the nano silver oxide-titanium dioxide complex can be evenly distributed in the polyester pre-oriented yarn system under the synergistic effect of dispersant and octadecylamine and then through ultrasonic dispersion, thereby enabling the prepared polyester pre-oriented yarn to have more lasting antibacterial properties.

[0017] Preferably, the heating temperature is 250-280°C.

[0018] Preferably, the method comprises the following specific steps: Depositing nano silver oxide on the surface of nano titanium dioxide by thermal deposition method to form a nano silver oxide-titanium dioxide composite, mixing the nano silver oxide-titanium dioxide composite with a dispersant, adding the composite to an octadecylamine solution, ultrasonically dispersing the composite, and drying the composite. Then, grinding the composite while adding a silane coupling agent to obtain a modified nano silver oxide-titanium dioxide composite; Terephthalic acid, isophthalic acid, silane coupling agent, ethylene glycol, modified nano silver oxide-titanium dioxide composite and nano silicon dioxide are mixed, heated and reacted to obtain a molten mixture, and the molten mixture is spun, cooled and stretched to obtain nano silver oxide modified polyester pre-oriented yarn.

[0019] In summary, this application has the following beneficial effects: 1. Since the present invention adopts the method of adding nano silver oxide in the reaction process of terephthalic acid and ethylene glycol, the silver ions can be stably added to the polyester pre-oriented yarn system, and the silver ions are slowly released, so that the polyester pre-oriented yarn has a more durable antibacterial effect. At the same time, the nano silver oxide is deposited and generated on the surface of the nano titanium dioxide, which can promote the uniform dispersion of the nano silver oxide in the polyester pre-oriented yarn system, and the silver ions are slowly released, thereby prolonging the antibacterial time of the polyester pre-oriented yarn. Octadecanamine forms a chemical bond with the surface of the polyester pre-oriented yarn by wet-modifying the nano silver oxide-titanium dioxide composite, thereby enhancing the stability and durability of the nano silver oxide-titanium dioxide composite in the polyester pre-oriented yarn system, improving the hydrophilicity of the polyester pre-oriented yarn, and thus improving the antibacterial durability and hygroscopicity of the polyester pre-oriented yarn.

[0020] 2. In the present application, isophthalic acid is used to modify the reaction of ethylene glycol and terephthalic acid, which can make the prepared polyester pre-oriented yarn have a better elongation at break, and at the same time is beneficial to the diffusion and adsorption of water molecules, thereby improving the hygroscopicity of the polyester pre-oriented yarn. DETAILED DESCRIPTION

[0021] The present application is further described in detail below with reference to the embodiments.

[0022] All raw materials in the examples are commercially available. Example

[0023] Example 1 The present embodiment provides a nano-silver oxide modified polyester pre-oriented yarn, comprising the following raw materials in parts by weight: 100 kg of terephthalic acid, 50 kg of ethylene glycol, 0.7 kg of nano-silicon dioxide, 2 kg of a matting agent, and 2 kg of a dispersant; wherein the dispersant is sodium hexametaphosphate, the matting agent is titanium dioxide, nano-silver oxide is deposited on the surface of titanium dioxide to form a nano-silver oxide-titanium dioxide composite, the loading amount of the nano-silver oxide is 5% of the mass of titanium dioxide, and the surface of the nano-silver oxide-titanium dioxide composite is wet-modified by octadecylamine.

[0024] The preparation method of nano silver oxide modified polyester pre-oriented yarn comprises the following specific steps: S1: titanium dioxide is immersed in a silver nitrate solution for 2 hours, dried at 80°C, calcined at 480°C for 1 hour, and fully ground to oxidize and deposit on the surface of nano-titanium dioxide to generate nano-silver oxide, wherein the average particle size of the nano-silver oxide is 15 nm, and the average particle size of the nano-titanium dioxide is 80 nm, thereby obtaining a nano-silver oxide-titanium dioxide composite; then the nano-silver oxide-titanium dioxide composite is mixed with 50% by mass of a dispersant, and added to an octadecylamine-ethanol solution, wherein the mass ratio of the octadecylamine-ethanol solution to the nano-silver oxide-titanium dioxide composite is 1:1, and the mass fraction of octadecylamine in the octadecylamine-ethanol solution is 50%, magnetic stirring is performed to uniformly disperse the nano-silver oxide-titanium dioxide composite by ultrasonication for 2 hours, and the nano-silver oxide-titanium dioxide composite is dried and ground to obtain a modified nano-silver oxide-titanium dioxide composite.

[0025] S2: terephthalic acid, ethylene glycol, modified nano silver oxide-titanium dioxide composite, nano silicon dioxide and the remaining 50% by mass of dispersant are mixed, heated to 270°C for reaction for 3.5 hours to obtain a molten mixture, and the molten mixture is spun, cooled and stretched to obtain nano silver oxide modified polyester pre-oriented yarn with a cross-shaped cross section.

[0026] Example 2 The difference between Example 2 and Example 1 is that the amount of terephthalic acid used in the nano-silver oxide modified polyester pre-oriented yarn raw material is 90 kg, the amount of ethylene glycol used is 40 kg, the amount of nano-silicon dioxide used is 0.8 kg, the amount of matting agent used is 1 kg, and the amount of dispersant used is 1 kg.

[0027] Example 3 The difference between Example 3 and Example 1 is that the amount of terephthalic acid used in the nano-silver oxide modified polyester pre-oriented yarn raw material is 110 kg, the amount of ethylene glycol used is 60 kg, the amount of nano-silicon dioxide used is 0.5 kg, the amount of matting agent used is 3 kg, and the amount of dispersant used is 3 kg.

[0028] Example 4 The difference between Example 4 and Example 1 is that the nano silver oxide modified polyester pre-oriented yarn raw material further includes 8 kg of isophthalic acid.

[0029] The preparation method of nano silver oxide modified polyester pre-oriented yarn comprises the following specific steps: S1: Titanium dioxide is immersed in a silver nitrate solution for 2 hours, dried at 80°C, calcined at 480°C for 1 hour, and fully ground, and then oxidized on the surface of nano-titanium dioxide to generate nano-silver oxide, wherein the average particle size of the nano-silver oxide is 15 nm, and the average particle size of the nano-titanium dioxide is 80 nm, thereby obtaining a nano-silver oxide-titanium dioxide composite; then the nano-silver oxide-titanium dioxide composite is mixed with 50% by mass of a dispersant, and added to an octadecylamine-ethanol solution, wherein the mass ratio of the octadecylamine-ethanol solution to the nano-silver oxide-titanium dioxide composite is 1:1, and the mass fraction of octadecylamine in the octadecylamine-ethanol solution is 50%, magnetic stirring is performed to uniformly disperse the nano-silver oxide-titanium dioxide composite by ultrasonication for 2 hours, and the nano-silver oxide-titanium dioxide composite is dried and ground to obtain a modified nano-silver oxide-titanium dioxide composite.

[0030] S2: terephthalic acid, ethylene glycol, isophthalic acid, modified nano silver oxide-titanium dioxide composite, nano silicon dioxide and the remaining 50% by mass of dispersant are mixed, heated to 270°C for reaction for 3.5 hours to obtain a molten mixture, and the molten mixture is spun, cooled and stretched to obtain nano silver oxide modified polyester pre-oriented yarn with a cross-shaped cross section.

[0031] Example 5 The difference between Example 5 and Example 4 is that the nano silver oxide modified polyester pre-oriented yarn raw material further includes 2 kg of silane coupling agent, which is KH-560.

[0032] The preparation method of nano silver oxide modified polyester pre-oriented yarn comprises the following specific steps: S1: titanium dioxide is immersed in a silver nitrate solution for 2 hours, dried at 80°C, calcined at 480°C for 1 hour, and fully ground, and then oxidized on the surface of nano-titanium dioxide to generate nano-silver oxide, wherein the average particle size of the nano-silver oxide is 15 nm, and the average particle size of the nano-titanium dioxide is 80 nm, thereby obtaining a nano-silver oxide-titanium dioxide composite; then the nano-silver oxide-titanium dioxide composite is mixed with 50% by mass of a dispersant, and added to an octadecylamine-ethanol solution, wherein the mass ratio of the octadecylamine-ethanol solution to the nano-silver oxide-titanium dioxide composite is 1:1, and the mass fraction of octadecylamine in the octadecylamine-ethanol solution is 50%, magnetic stirring is performed to uniformly disperse the composite by ultrasonication for 2 hours, and after drying, a silane coupling agent is added while grinding to obtain a modified nano-silver oxide-titanium dioxide composite.

[0033] S2: terephthalic acid, ethylene glycol, isophthalic acid, modified nano silver oxide-titanium dioxide composite, nano silicon dioxide and the remaining 50% by mass of dispersant are mixed, heated to 270°C for reaction for 3.5 hours to obtain a molten mixture, and the molten mixture is spun, cooled and stretched to obtain nano silver oxide modified polyester pre-oriented yarn with a cross-shaped cross section.

[0034] Example 6 The difference between Example 6 and Example 5 is that the amount of isophthalic acid used in the nano-silver oxide modified polyester pre-oriented yarn raw material is 5 kg, and the amount of silane coupling agent used is 3 kg.

[0035] Example 7 The difference between Example 7 and Example 5 is that the amount of isophthalic acid used in the nano-silver oxide modified polyester pre-oriented yarn raw material is 10 kg, and the amount of silane coupling agent used is 1 kg.

[0036] Example 8 The difference between Example 8 and Example 5 is that the nano silver oxide modified polyester pre-oriented yarn has a circular cross section.

[0037] Comparative Example Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the method for preparing nano silver oxide modified polyester pre-oriented yarn comprises the following specific steps: Terephthalic acid, ethylene glycol, nano silver oxide, nano titanium dioxide, nano silicon dioxide and a dispersant are mixed, the mass ratio of nano silver oxide to nano titanium dioxide is 1:1, and the mixture is heated to 270°C for reaction for 3.5 hours to obtain a molten mixture. The molten mixture is spun, cooled and stretched to obtain nano silver oxide-modified polyester pre-oriented yarn with a cross-shaped cross section.

[0038] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that the method for preparing nano silver oxide modified polyester pre-oriented yarn comprises the following specific steps: S1: The titanium dioxide is immersed in a silver nitrate solution for 2 hours, dried at 80°C, calcined at 480°C for 1 hour, and fully ground to oxidize the surface of the nano-titanium dioxide to generate nano-silver oxide, the average particle size of the nano-silver oxide is 15nm, and the average particle size of the nano-titanium dioxide is 80nm, thereby obtaining a nano-silver oxide-titanium dioxide composite.

[0039] S2: terephthalic acid, ethylene glycol, nano silver oxide-titanium dioxide composite, nano silicon dioxide and the remaining 50% by mass of the dispersant are mixed, heated to 270° C. for reaction for 3.5 hours to obtain a molten mixture, and the molten mixture is spun, cooled and stretched to obtain nano silver oxide-modified polyester pre-oriented yarn with a cross-shaped cross section.

[0040] Performance testing According to the nano silver oxide modified polyester pre-oriented yarn provided in Examples 1-8 and Comparative Examples 1-2 of the present application, the following performance tests were performed, and the specific test results are shown in Table 1.

[0041] Detection Methods 1. Antibacterial properties With reference to the standard of GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles Part 3", the bacterial species are Staphylococcus aureus, Escherichia coli and Candida albicans, the average antibacterial rates of the three bacterial species are calculated, and the antibacterial properties of the nano-silver oxide modified polyester pre-oriented yarn prepared in this application are tested, as well as the antibacterial properties after washing 50 times.

[0042] 2. Elongation at break Referring to the standard of GB / T 14344-2022 "Test method for tensile properties of chemical fiber filaments", the YG023B-Ⅱ fully automatic single yarn strength tester was used to test the elongation at break of the nano-silver oxide modified polyester pre-oriented yarn prepared in this application.

[0043] 3. Hygroscopicity With reference to the standard of GB / T 21655.1-2008 "Evaluation of Moisture Absorption and Quick-Drying Properties of Textiles", the fiber fabric woven from the nano silver oxide modified polyester pre-oriented yarn prepared in the present application was tested, and the water absorption rate of the fiber plant was tested.

[0044] Table 1: Performance test results data table It can be seen from the performance test results that the antibacterial activity of the polyester pre-oriented yarn prepared in this application is durable, and it also maintains good moisture absorption effect and elongation at break, which is convenient for subsequent stretching and weaving. By comparing Example 1 with Comparative Examples 1-2, it can be seen that Comparative Example 1 directly adds nano silver oxide and titanium dioxide to the polyester pre-oriented yarn raw material, and Comparative Example 2 does not use octadecylamine for wet modification. From the performance test results, it can be seen that although the prepared polyester pre-oriented yarn still has good antibacterial properties, the antibacterial durability is significantly reduced. Further explanation of the polyester pre-oriented yarn prepared in this application, titanium dioxide is used as a carrier of nano silver oxide, and octadecylamine is used for wet modification. The stability of the antibacterial active ingredients in the polyester pre-oriented yarn is enhanced through a dual process, and the antibacterial active ingredients are prevented from falling off during processing and use, thereby improving the durability of the antibacterial effect of the polyester pre-oriented yarn.

[0045] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A nano silver oxide modified polyester pre-oriented yarn, characterized in that: The invention comprises the following raw materials in parts by weight: 90-110 parts of terephthalic acid, 40-60 parts of ethylene glycol, 0.5-0.8 parts of nano silicon dioxide, 1-3 parts of a matting agent and 1-3 parts of a dispersant; the matting agent is nano titanium dioxide, nano silver oxide is deposited on the surface of the nano titanium dioxide to form a nano silver oxide-titanium dioxide composite, and the surface of the nano silver oxide-titanium dioxide composite is wet-modified by octadecylamine.

2. The nano silver oxide modified polyester pre-oriented yarn according to claim 1, characterized in that: The polyester pre-oriented yarn raw material also includes 5-10 parts of isophthalic acid and 1-3 parts of a silane coupling agent.

3. The nano silver oxide modified polyester pre-oriented yarn according to claim 1, characterized in that: The dispersant is sodium hexametaphosphate.

4. The nano silver oxide modified polyester pre-oriented yarn according to claim 1, characterized in that: The particle size of the nano silver oxide is 10-25 nm, and the particle size of the titanium dioxide is 50-100 nm.

5. The nano silver oxide modified polyester pre-oriented yarn according to claim 1, characterized in that: The polyester pre-oriented yarn has a special-shaped cross section, and the special-shaped cross section is a cross-shaped cross section.

6. A method for preparing nano silver oxide modified polyester pre-oriented yarn according to any one of claims 1 to 5, characterized in that: The specific steps include: Depositing nano silver oxide on the surface of nano titanium dioxide by thermal deposition method to form a nano silver oxide-titanium dioxide composite, mixing the nano silver oxide-titanium dioxide composite with a dispersant, adding the composite to an octadecylamine solution, ultrasonically dispersing the composite, and drying the composite. Then, grinding the composite while adding a silane coupling agent to obtain a modified nano silver oxide-titanium dioxide composite; Terephthalic acid, ethylene glycol, modified nano silver oxide-titanium dioxide composite and nano silicon dioxide are mixed, heated and reacted to obtain a molten mixture, and the molten mixture is spun, cooled and stretched to obtain nano silver oxide modified polyester pre-oriented yarn.

7. The method for preparing nano silver oxide modified polyester pre-oriented yarn according to claim 6, characterized in that: The heating temperature is 250-280°C.

8. The method for preparing nano silver oxide modified polyester pre-oriented yarn according to claim 6, characterized in that: The specific steps include: Depositing nano silver oxide on the surface of nano titanium dioxide by thermal deposition method to form a nano silver oxide-titanium dioxide composite, mixing the nano silver oxide-titanium dioxide composite with a dispersant, adding the composite to an octadecylamine solution, ultrasonically dispersing the composite, and drying the composite. Then, grinding the composite while adding a silane coupling agent to obtain a modified nano silver oxide-titanium dioxide composite; Terephthalic acid, isophthalic acid, silane coupling agent, ethylene glycol, modified nano silver oxide-titanium dioxide composite and nano silicon dioxide are mixed, heated and reacted to obtain a molten mixture, and the molten mixture is spun, cooled and stretched to obtain nano silver oxide modified polyester pre-oriented yarn.

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