High-wear-resistance polyurethane fiber composite yarn and preparation method thereof

Abstract

The application discloses a kind of high wear-resistant chinlon polyester fiber composite yarn and preparation method thereof, it is related to textile field, the high wear-resistant chinlon polyester fiber composite yarn of the application is spun by chinlon fiber and modified polyester fiber according to mass ratio 50-60:40-50;The modified polyester fiber includes the following weight parts of raw materials: dimethyl terephthalate 45-50 parts, antistatic monomer 5-8 parts, ethylene glycol 18-22 parts, metal acetate catalyst 0.08-0.12 parts, antimony catalyst 0.1-0.2 parts;Wherein antistatic monomer is obtained by nucleophilic acyl substitution reaction using 2,6-diquinoline diol and 6-chloro carbonyl-2-naphthalene formate to obtain heat-resistant intermediate, then heat-resistant intermediate and 1-chlorododecane are reacted to obtain antistatic monomer.

Description

Technical Field

[0001] This invention belongs to the field of textile technology, specifically relating to a high abrasion-resistant nylon-polyester fiber composite yarn. Background Technology

[0002] Nylon and polyester are both widely used synthetic fibers in the textile industry. Nylon has excellent abrasion resistance, elasticity, and moisture absorption, but it has disadvantages such as low modulus, poor dimensional stability, and insufficient heat resistance. Polyester, on the other hand, has advantages such as high strength, high modulus, and good dimensional stability, but its abrasion resistance and moisture absorption are relatively poor. Combining the two to prepare composite yarns can combine the characteristics of nylon and polyester, and can be widely used in sportswear, outdoor equipment, medical protective equipment, and infant textiles.

[0003] However, nylon and polyester are thermodynamically incompatible systems with weak interfacial bonding. During stretching, friction, and heat setting, interfacial peeling and splitting easily occur, leading to a significant decrease in the abrasion resistance and service life of the composite yarn. Existing methods to improve interfacial compatibility mainly include adding block copolymer compatibilizers and plasma or chemical etching treatment of the fiber surface, but these methods can easily damage the fiber's intrinsic properties. Meanwhile, conventional nylon-polyester composite yarns generally suffer from core defects such as insufficient antistatic properties and lack of antibacterial function. Static electricity easily accumulates on the fiber surface due to friction, leading to phenomena such as static adsorption, pilling, and fuzzing, affecting product appearance and user experience, and posing safety hazards in special applications such as medical and electronic applications. Furthermore, the lack of effective antibacterial function makes it easy for bacteria to grow, producing odors and harming human health, failing to meet the stringent requirements of close-fitting protection and medical scenarios. The poor interfacial compatibility further affects the long-term effectiveness of antistatic and antibacterial functions, restricting the high-end application of composite yarns.

[0004] Currently, imparting antibacterial and antistatic properties to textiles mainly involves adding compatibilizers, surface modification, or finishing processes. Finishing methods, such as padding and coating, attach antibacterial or antistatic agents to the surface of fibers or fabrics. While simple and widely applicable, these methods generally suffer from poor functional durability, insufficient wash resistance, and easy migration and precipitation of auxiliaries. Blending involves melt-blending functional auxiliaries with fiber-forming polymers before spinning, which can improve functional durability to some extent. However, antibacterial and antistatic agents are often inorganic nanoparticles or small organic molecules, which have poor compatibility with the polymer matrix, easily leading to aggregation and migration, affecting spinning stability and fiber mechanical properties. Furthermore, the functional components are often embedded within the fiber, resulting in insufficient efficiency. Summary of the Invention

[0005] To address the shortcomings mentioned in the background art, the present invention aims to provide a high abrasion-resistant nylon-polyester fiber composite yarn and its preparation method. The method utilizes antistatic monomers to modify polyester fibers, thereby endowing the composite yarn with antibacterial and antistatic properties, and improving the yarn's abrasion and heat resistance.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A high abrasion-resistant nylon-polyester composite yarn is spun from nylon fiber and modified polyester fiber at a mass ratio of 50-60:40-50.

[0008] Modified polyester fiber comprises the following raw materials in parts by weight: 45-50 parts dimethyl terephthalate, 5-8 parts antistatic monomer, 18-22 parts ethylene glycol, 0.08-0.12 parts metal acetate catalyst, and 0.1-0.2 parts antimony catalyst;

[0009] The antistatic monomer is obtained by reacting 2,6-diquinolinediol with methyl 6-chlorocarbonyl-2-naphthoic acid via a nucleophilic acyl substitution reaction to obtain a heat-resistant intermediate, and then reacting the heat-resistant intermediate with 1-chlorododecane as a quaternary ammonium salt to obtain the antistatic monomer.

[0010] More preferably, the metal acetate catalyst is zinc acetate or calcium acetate.

[0011] More preferably, the antimony-based catalyst is antimony trioxide or antimony glycol.

[0012] More preferably, the method for preparing the antistatic monomer includes the following steps:

[0013] S1. Take 2,6-diquinolinediol and acid-binding agent into a reactor, add dichloromethane, stir in a cold water bath for 10-20 min, then add dropwise a mixture of methyl 6-chlorocarbonyl-2-naphthoic acid ester and dichloromethane. After the addition is complete, continue stirring the reaction at room temperature for 50-60 min. After the reaction is complete, quench the reaction solution with saturated sodium bicarbonate solution, then extract the quenched mixture with ethyl acetate and retain the organic phase. Then wash the organic phase with saturated brine and dry and rotary evaporate to obtain a heat-resistant intermediate.

[0014] S2. Add the heat-resistant intermediate, 1-chlorododecane and acetonitrile to the reactor, heat to 60-70℃, react for 16-24h and then cool to room temperature. Wash the product with petroleum ether, filter and retain the solid. Then dry the obtained solid to obtain the antistatic monomer.

[0015] More preferably, the acid-binding agent in step S1 is triethylamine or pyridine.

[0016] More preferably, in step S1, the addition ratio of 2,6-diquinolinediol to the acid-binding agent is 2-3g:2-6mL.

[0017] More preferably, in step S1, the addition ratio of methyl 6-chlorocarbonyl-2-naphthoic acid ester to dichloromethane in the mixture of methyl 6-chlorocarbonyl-2-naphthoic acid ester and dichloromethane is 6-10 g: 10-15 mL.

[0018] More preferably, the addition ratio of the heat-resistant intermediate and 1-chlorododecane in step S2 is 5.3-8.8 g: 1.8-3 mL.

[0019] A method for preparing a high abrasion-resistant nylon-polyester fiber composite yarn includes the following steps:

[0020] Step 1: Dimethyl terephthalate, antistatic monomer, ethylene glycol, metal acetate catalyst, and antimony catalyst are placed in a reactor. The temperature is raised to 180-200℃ under a nitrogen atmosphere and the reaction is kept at a constant temperature for 2-4 hours. After the reaction is completed, the temperature is raised to 250-260℃, and the system is evacuated for pre-polymerization. Polycondensation is completed after 5-6 hours. The modified copolyester is obtained by vacuum drying at 90-100℃ for 10-12 hours. The modified copolyester is added to a screw extruder for melt extrusion, and then spun, cooled, and wound to obtain modified polyester fibers.

[0021] The second step involves initially opening and mixing the modified polyester fiber and nylon fiber, then processing the mixed fibers into a uniform sliver through a carding process. This sliver is then drawn and stretched to ensure uniform longitudinal and transverse distribution. Finally, the uniformly mixed fiber sliver is stretched and twisted to spin a composite yarn.

[0022] More preferably, the temperature of melt extrusion in the first step is 260-280℃.

[0023] The beneficial effects of this invention are:

[0024] The antistatic monomer of this invention, as a product of the quaternary ammonium salt reaction, has a positively charged quaternary ammonium salt group in its molecular structure that can specifically bind to the negatively charged bacterial cell membrane, disrupting the cell membrane's integrity. It can also penetrate the cell interior through osmosis, interfering with intracellular enzyme activity, protein synthesis, and metabolic processes, ultimately leading to bacterial death or loss of reproductive capacity. Because the quaternary ammonium salt structure is covalently fixed to the polyester backbone, it is not easily detached, thus enabling the composite yarn to achieve a long-lasting antibacterial effect. Furthermore, the quaternary ammonium salt cations can provide charge carriers for ionization, maintaining charge balance under the influence of an electric field, endowing the composite yarn with antistatic properties and reducing static electricity adsorption and pilling during use.

[0025] After the antistatic monomer is covalently introduced into the polyester backbone, the polycyclic aromatic rings in the molecular structure can effectively restrain the movement of macromolecular chain segments, thereby increasing the glass transition temperature and bulk heat resistance of the modified polyester. This suppresses chain slippage and thermal shrinkage deformation under high-temperature conditions, thus improving the heat resistance of the composite yarn.

[0026] At the same time, quaternary ammonium cations can generate strong ion-dipole interactions with the polar amide groups in the nylon molecular chain, improving the interfacial bonding strength between the polyester and nylon phases. The flexible long-chain alkyl groups in the polyester side chain effectively reduce the interfacial stress between the two phases, improve the interfacial compatibility between polyester fiber and nylon, and reduce interfacial peeling and breakage of composite yarns during stretching and friction, thereby improving the wear resistance of composite yarns. Detailed Implementation

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0028] The CAS classification number of methyl 6-chlorocarbonyl-2-naphthoic acid involved in the following examples is 69008-41-9.

[0030] Example 1

[0031] A high abrasion-resistant nylon-polyester composite yarn is spun from nylon fiber and modified polyester fiber at a mass ratio of 60:40. The modified polyester fiber includes the following raw materials in parts by weight: 45 parts dimethyl terephthalate, 5 parts antistatic monomer, 18 parts ethylene glycol, 0.08 parts zinc acetate, and 0.1 parts antimony trioxide.

[0032] The antistatic monomer is produced by the following steps:

[0033] S1. Take 2g of 2,6-diquinolinediol and 2mL of pyridine into a reactor, add 20mL of dichloromethane, stir in a cold water bath for 10min, then add dropwise a mixture of 6g of methyl 6-chlorocarbonyl-2-naphthoic acid ester and 10mL of dichloromethane. After the addition is complete, continue stirring at room temperature for 50min. After the reaction is complete, quench the reaction solution with saturated sodium bicarbonate solution, then extract the quenched mixture with ethyl acetate and retain the organic phase. Then wash the organic phase with saturated brine and dry and rotary evaporate to obtain a heat-resistant intermediate.

[0034] S2. Add 5.3g of heat-resistant intermediate, 1.8mL of 1-chlorododecane and 35mL of acetonitrile to the reactor, heat to 60℃, react for 24h and then cool to room temperature. Wash the product with petroleum ether, filter and retain the solid. Then dry the obtained solid to obtain the antistatic monomer.

[0035] A method for preparing a high abrasion-resistant nylon-polyester fiber composite yarn includes the following steps:

[0036] Step 1: Take 45g of dimethyl terephthalate, 5g of antistatic monomer, 18g of ethylene glycol, 0.08g of zinc acetate, and 0.1g of antimony trioxide into a reactor. Under a nitrogen atmosphere, heat to 180℃ and react at a constant temperature for 4 hours. After the reaction is completed, raise the temperature to 250℃ and vacuum the system for pre-polymerization. After 6 hours, the polymerization is completed. After vacuum drying at 90℃ for 12 hours, a modified copolyester is obtained. The modified copolyester is added to a screw extruder and melt-extruded at 260℃. After spinning, cooling, and winding, modified polyester fibers are obtained.

[0037] The second step involves initially opening and mixing 40g of modified polyester fiber and 60g of nylon fiber, then processing the mixed fibers into a uniform sliver through a carding process, followed by drawing and stretching to ensure uniform longitudinal and transverse distribution of the yarn. Finally, the uniformly mixed fiber sliver is stretched and twisted to spin a composite yarn.

[0038] Example 2

[0039] A high abrasion-resistant nylon-polyester composite yarn is spun from nylon fiber and modified polyester fiber at a mass ratio of 50:50. The modified polyester fiber includes the following raw materials in parts by weight: 50 parts dimethyl terephthalate, 8 parts antistatic monomer, 22 parts ethylene glycol, 0.12 parts calcium acetate, and 0.2 parts antimony glycol.

[0040] The antistatic monomer is produced by the following steps:

[0041] S1. Take 3g of 2,6-diquinolinediol and 6mL of triethylamine into a reactor, add 40mL of dichloromethane, stir in a cold water bath for 20min, then add dropwise a mixture of 10g of methyl 6-chlorocarbonyl-2-naphthoic acid ester and 15mL of dichloromethane. After the addition is complete, continue stirring at room temperature for 60min. After the reaction is complete, quench the reaction solution with saturated sodium bicarbonate solution, then extract the quenched mixture with ethyl acetate and retain the organic phase. Then wash the organic phase with saturated brine and dry and rotary evaporate to obtain a heat-resistant intermediate.

[0042] S2. Add 8.8g of heat-resistant intermediate, 3mL of 1-chlorododecane and 50mL of acetonitrile to the reactor, heat to 70℃, react for 16h and then cool to room temperature. Wash the product with petroleum ether, filter and retain the solid. Then dry the obtained solid to obtain the antistatic monomer.

[0043] A method for preparing a high abrasion-resistant nylon-polyester fiber composite yarn includes the following steps:

[0044] Step 1: Take 50g of dimethyl terephthalate, 8g of antistatic monomer, 22g of ethylene glycol, 0.12g of calcium acetate, and 0.2g of antimony glycol in a reactor. Heat the reactor to 200℃ under a nitrogen atmosphere and react at a constant temperature for 2 hours. After the reaction is complete, raise the temperature to 260℃ and vacuum the system for pre-polymerization. After 5 hours, the pre-polymerization is completed. After vacuum drying at 100℃ for 10 hours, a modified copolyester is obtained. Add the modified copolyester to a screw extruder and melt extrude it at 280℃. After spinning, cooling, and winding, the modified polyester fiber is obtained.

[0045] The second step involves initially opening and mixing 50g of modified polyester fiber and 50g of nylon fiber, then processing the mixed fibers into a uniform sliver through a carding process, followed by drawing and stretching to ensure uniform longitudinal and transverse distribution of the yarn. Finally, the uniformly mixed fiber sliver is stretched and twisted to spin a composite yarn.

[0046] Example 3

[0047] A high abrasion-resistant nylon-polyester composite yarn is spun from nylon fiber and modified polyester fiber at a mass ratio of 55:45. The modified polyester fiber includes the following raw materials in parts by weight: 48 parts dimethyl terephthalate, 7 parts antistatic monomer, 20 parts ethylene glycol, 0.10 parts zinc acetate, and 0.15 parts antimony glycol.

[0048] The antistatic monomer is produced by the following steps:

[0049] S1. Take 2.5g of 2,6-diquinolinediol and 4mL of pyridine into a reactor, add 30mL of dichloromethane, stir in a cold water bath for 15min, then add dropwise a mixture of 8g of methyl 6-chlorocarbonyl-2-naphthoic acid ester and 13mL of dichloromethane. After the addition is complete, continue stirring at room temperature for 55min. After the reaction is complete, quench the reaction solution with saturated sodium bicarbonate solution, then extract the quenched mixture with ethyl acetate and retain the organic phase. Then wash the organic phase with saturated brine and dry and rotary evaporate to obtain a heat-resistant intermediate.

[0050] S2. Add 7.2g of heat-resistant intermediate, 2.4mL of 1-chlorododecane and 40mL of acetonitrile to the reactor, heat to 65℃, react for 20h and then cool to room temperature. Wash the product with petroleum ether, filter and retain the solid. Then dry the obtained solid to obtain the antistatic monomer.

[0051] A method for preparing a high abrasion-resistant nylon-polyester fiber composite yarn includes the following steps:

[0052] Step 1: Take 48g of dimethyl terephthalate, 7g of antistatic monomer, 20g of ethylene glycol, 0.1g of zinc acetate, and 0.15g of antimony glycol in a reactor. Heat to 190℃ under a nitrogen atmosphere and react at a constant temperature for 3 hours. After the reaction is completed, raise the temperature to 255℃ and evacuate the system for pre-polymerization. Polycondensation ends after 5.5 hours. After vacuum drying at 95℃ for 11 hours, a modified copolyester is obtained. The modified copolyester is added to a screw extruder and melt-extruded at 270℃. After spinning, cooling, and winding, modified polyester fibers are obtained.

[0053] The second step involves initially opening and mixing 45g of modified polyester fiber and 55g of nylon fiber, then processing the mixed fibers into a uniform sliver through a carding process, followed by drawing and stretching to ensure uniform longitudinal and transverse distribution of the yarn. Finally, the uniformly mixed fiber sliver is stretched and twisted to spin a composite yarn.

[0054] Comparative Example 1

[0055] A high abrasion-resistant nylon-polyester composite yarn is spun from nylon fiber and polyester fiber at a mass ratio of 55:45. The polyester fiber includes the following raw materials in parts by weight: 48 parts dimethyl terephthalate, 20 parts ethylene glycol, 0.10 parts zinc acetate, and 0.15 parts antimony glycol.

[0056] A method for preparing a high abrasion-resistant nylon-polyester fiber composite yarn includes the following steps:

[0057] Step 1: Take 48g of dimethyl terephthalate, 20g of ethylene glycol, 0.1g of zinc acetate, and 0.15g of antimony glycol in a reactor. Heat the reactor to 190℃ under a nitrogen atmosphere and react at a constant temperature for 3 hours. After the reaction is complete, raise the temperature to 255℃ and vacuum the system for pre-polymerization. Polycondensation is completed after 5.5 hours. After vacuum drying at 95℃ for 11 hours, a polyester copolymer is obtained. The polyester copolymer is added to a screw extruder and melt-extruded at 270℃. After spinning, cooling, and winding, polyester fibers are obtained.

[0058] The second step involves initially opening and mixing 45g of polyester fiber and 55g of nylon fiber, then processing the mixed fibers into a uniform sliver through a carding process. This sliver is then drawn and stretched to ensure uniform longitudinal and transverse distribution. Finally, the uniformly mixed fiber sliver is stretched and twisted to spin a composite yarn.

[0059] Performance testing

[0060] Antibacterial performance: The antibacterial rate of each group of composite yarns against Staphylococcus aureus and Escherichia coli was tested according to GB / T20944.3-2008. The composite yarn in Comparative Example 1 was a blank control. The antibacterial performance monitoring data are shown in Table 1.

[0061]

[0062] As can be seen from Table 1, Examples 1-3 all showed significant antibacterial effects against Escherichia coli and Staphylococcus aureus, indicating that modifying polyester fibers endowed the composite yarn with antibacterial properties.

[0063] Heat resistance, abrasion resistance, and antistatic properties: The dry heat shrinkage rate of each group of composite yarns at 120-150℃ was tested according to GB / T6505-2017. Abrasion resistance tests were conducted on the composite yarns using a reciprocating abrasion tester (FZ / T 01058-1999) with a 35g tension weight and 400 grit sandpaper. The number of friction cycles at breakage was recorded. The half-life of each group of composite yarns was monitored in real-time using a non-contact electrostatic voltage probe via high-voltage corona discharge, according to GB / T 12703.1-2021. The obtained monitoring data for heat resistance, abrasion resistance, and antistatic properties are shown in Table 2.

[0064] Table 2: Statistical Table of Monitoring Data for Heat Resistance, Wear Resistance and Antistatic Properties

[0065]

[0066] As can be seen from Table 2, compared with Comparative Example 1, Examples 1-3 have lower dry heat shrinkage, more friction times at break, and shorter half-life. This shows that modifying polyester fibers can improve the heat resistance, abrasion resistance, and antistatic properties of composite yarns.

[0067] The foregoing has provided a detailed description of one embodiment of the present invention, but this description is merely a preferred embodiment and should not be construed as limiting the scope of the invention. All equivalent variations and modifications made within the scope of the claims of this invention should still fall within the patent coverage of this invention.

Claims

1. A high abrasion-resistant nylon-polyester fiber composite yarn, characterized in that, The high abrasion-resistant nylon-polyester composite yarn is spun from nylon fiber and modified polyester fiber at a mass ratio of 50-60:40-50. The modified polyester fiber comprises the following raw materials in parts by weight: 45-50 parts of dimethyl terephthalate, 5-8 parts of antistatic monomer, 18-22 parts of ethylene glycol, 0.08-0.12 parts of metal acetate catalyst, and 0.1-0.2 parts of antimony catalyst; The antistatic monomer is obtained by reacting 2,6-diquinolinediol with methyl 6-chlorocarbonyl-2-naphthoic acid via a nucleophilic acyl substitution reaction to obtain a heat-resistant intermediate, and then reacting the heat-resistant intermediate with 1-chlorododecane as a quaternary ammonium salt to obtain the antistatic monomer.

2. The high abrasion-resistant nylon-polyester fiber composite yarn according to claim 1, characterized in that, The metal acetate catalyst is zinc acetate or calcium acetate.

3. The high abrasion-resistant nylon-polyester fiber composite yarn according to claim 1, characterized in that, The antimony-based catalyst is antimony trioxide or antimony glycol.

4. The high abrasion-resistant nylon-polyester fiber composite yarn according to claim 1, characterized in that, The method for preparing the antistatic monomer includes the following steps: S1. Take 2,6-diquinolinediol and acid-binding agent into a reactor, add dichloromethane, stir in a cold water bath for 10-20 min, then add dropwise a mixture of methyl 6-chlorocarbonyl-2-naphthoic acid ester and dichloromethane. After the addition is complete, continue stirring the reaction at room temperature for 50-60 min. After the reaction is complete, quench the reaction solution with saturated sodium bicarbonate solution, then extract the quenched mixture with ethyl acetate and retain the organic phase. Then wash the organic phase with saturated brine and dry and rotary evaporate to obtain a heat-resistant intermediate. S2. Add the heat-resistant intermediate, 1-chlorododecane and acetonitrile to the reactor, heat to 60-70℃, react for 16-24h and then cool to room temperature. Wash the product with petroleum ether, filter and retain the solid. Then dry the obtained solid to obtain the antistatic monomer.

5. The high abrasion-resistant nylon-polyester fiber composite yarn according to claim 4, characterized in that, The acid-binding agent in step S1 is triethylamine or pyridine.

6. The high abrasion-resistant nylon-polyester fiber composite yarn according to claim 4, characterized in that, In step S1, the addition ratio of 2,6-diquinolinediol to the acid-binding agent is 2-3g:2-6mL.

7. The high abrasion-resistant nylon-polyester fiber composite yarn according to claim 4, characterized in that, In step S1, the ratio of methyl 6-chlorocarbonyl-2-naphthoic acid ester to dichloromethane in the mixture is 6-10 g: 10-15 mL.

8. The high abrasion-resistant nylon-polyester fiber composite yarn according to claim 4, characterized in that, In step S2, the addition ratio of the heat-resistant intermediate and 1-chlorododecane is 5.3-8.8 g: 1.8-3 mL.

9. A method for preparing a high abrasion-resistant nylon-polyester fiber composite yarn according to any one of claims 1-8, characterized in that, Includes the following steps: Step 1: Dimethyl terephthalate, antistatic monomer, ethylene glycol, metal acetate catalyst, and antimony catalyst are placed in a reactor. The temperature is raised to 180-200℃ under a nitrogen atmosphere and the reaction is kept at a constant temperature for 2-4 hours. After the reaction is completed, the temperature is raised to 250-260℃, and the system is evacuated for pre-polymerization. Polycondensation is completed after 5-6 hours. The modified copolyester is obtained by vacuum drying at 90-100℃ for 10-12 hours. The modified copolyester is added to a screw extruder for melt extrusion, and then spun, cooled, and wound to obtain modified polyester fibers. The second step involves initially opening and mixing the modified polyester fiber and nylon fiber, then processing the mixed fibers into a uniform sliver through a carding process. This sliver is then drawn and stretched to ensure uniform longitudinal and transverse distribution. Finally, the uniformly mixed fiber sliver is stretched and twisted to spin a composite yarn.

10. The method for preparing a high abrasion-resistant nylon-polyester fiber composite yarn according to claim 9, characterized in that, The temperature of melt extrusion in the first step is 260-280℃.

Images