Nylon spinning master batch as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of polymer functional material preparation, and particularly discloses a chinlon spinning master batch and a preparation method and application thereof.The preparation method comprises the following steps that S1, tourmaline powder, an antibacterial agent and acetic acid are sequentially added into a 90% caprolactam aqueous solution in proportion and stirred, and a mixed material is obtained; s2, transferring the mixed material obtained in the step S1 into a polymerization kettle, heating to 140-160 DEG C under the protection of nitrogen, carrying out prepolymerization reaction for 0.5-2 hours, and heating to carry out polymerization reaction, so as to obtain nylon 6 slices; and S3, cooling the nylon 6 slices obtained in the S2 to room temperature, cutting the nylon 6 slices into sheet-shaped coarse master batches with the thickness of 2-3mm, soaking the sheet-shaped coarse master batches in 75-85 hot water for 3-5 hours, and drying the sheet-shaped coarse master batches to obtain the chinlon spinning master batches. According to the chinlon spinning master batch and the preparation method and application thereof, the anion, far infrared and antibacterial properties are synergistic, the performance is balanced, and the chinlon spinning master batch is suitable for industrial production.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer functional material preparation, in particular to a polyamide spinning master batch and a preparation method and application thereof. BACKGROUND

[0002] Polyamide (also known as caprolactam or nylon 6) is an excellent engineering plastic with high mechanical strength, good wear resistance, good elasticity, excellent processing performance, and is widely used in clothing, home textiles, industrial textiles and other fields. With the increasing demand for material functionalization, polyamide fibers with both basic performance and functionality (such as negative ions, antibacterial properties, etc.) have become the development direction of the industry. Among them, negative ions have the health benefits of improving air quality and relieving fatigue, and tourmaline is a natural mineral with the characteristics of continuously releasing negative oxygen ions and far infrared radiation. The combination of tourmaline and nylon 6 can endow the material with health functionality and expand the application scenarios of nylon 6 in the high-end textile field.

[0003] In the prior art, the combination of tourmaline and nylon 6 is mostly achieved by melt blending. The polarity of the surface of the tourmaline particles is quite different from the non-polar segments of nylon 6, and the interface compatibility is poor, which leads to uneven dispersion of the particles in the nylon matrix and easy agglomeration. Moreover, the particles and the matrix are only physically mixed, and the bonding force is weak, which makes the particles easy to fall off during subsequent processing or use, affecting the functional stability and the mechanical properties of the material. In addition, the agglomerated tourmaline particles can damage the regularity of the molecular chains of nylon 6, resulting in a decrease in the mechanical strength of the material.

[0004] Therefore, it is crucial to achieve uniform dispersion and stable combination of tourmaline functional particles in nylon 6, so that the polyamide fiber master batch has excellent and stable antibacterial properties. SUMMARY

[0005] The purpose of the present application is to provide a polyamide spinning master batch and a preparation method and application thereof, which have synergistic effects of negative ions, far infrared and antibacterial properties, balanced performance, and are suitable for industrial production.

[0006] To achieve the above-mentioned purpose, the present application provides a preparation method of a polyamide spinning master batch, comprising the following steps: S1. Add tourmaline powder, antibacterial agent and acetic acid to the 90% caprolactam aqueous solution in proportion, and stir to obtain a uniformly dispersed mixture; S2. Transfer the mixture obtained in S1 to a polymerization kettle, heat to 140~160 under nitrogen protection, pre-polymerize for 0.5~2h, and then increase the temperature for polymerization to obtain nylon 6 chips. At this time, the caprolactam is completely polymerized to form polyamide 6 molecular chains, and the hydroxyl groups on the surface of the tourmaline and the active groups on the surface of the nano-zinc oxide are chemically bonded to the end groups of the polyamide molecular chains; S3. Cool the nylon 6 chips obtained in S2 to room temperature, cut them into sheet-like coarse masterbatches with a thickness of 2-3 mm, and place them at 75-85°C. Soak in hot water for 3-5 hours to remove unreacted caprolactam oligomers and prevent oligomer volatilization during spinning, which could cause fiber bubbles. Dry the masterbatch and control the moisture content to <0.1%. Low moisture content can prevent the fibers from breaking during spinning, thus obtaining nylon spinning masterbatch.

[0007] A 90% caprolactam aqueous solution provides the molecular chain backbone of nylon, tourmaline powder has both negative ion release and far-infrared radiation functions, zinc oxide can inhibit Escherichia coli and Staphylococcus aureus, has high safety and no migration, and acetic acid is used as a capping agent to control the degree of polymerization of nylon and optimize the melt flowability of masterbatch.

[0008] Preferably, in S1, the 90% caprolactam aqueous solution specifically comprises: Mix caprolactam and deionized water at a mass ratio of 9:1, 45~55 Stir and dissolve to obtain a 90% caprolactam aqueous solution; The tourmaline powder specifically refers to: After crushing the tourmaline mineral, ball milling was performed for 1.5–3 hours, followed by sieving to obtain a particle size of 0.5–8 μm. m tourmaline powder; The antibacterial agent is zinc oxide with a particle size of 50-200 nm. The zinc oxide is placed in a 1 wt% silane coupling agent-ethanol solution and stirred for 0.5-2 h. It is then sonicated in a constant temperature ultrasonic instrument at 55-65℃ for 5-15 min, heated to 75-80℃, and stirred until all the ethanol evaporates. Finally, it is transferred to an oven at 85-90℃ and dried for at least 2 h to prevent the antibacterial agent from agglomerating.

[0009] Preferably, in S1, the ratio of caprolactam, tourmaline powder, zinc oxide and acetic acid is 100g:25g:2~5g:0.5mL.

[0010] Preferably, in S1, the stirring specifically involves: Between 45 and 55 Stir for 20-40 minutes at a speed of 500-800 r / min.

[0011] Preferably, in S2, the prepolymerization reaction specifically comprises: Transfer the mixture to a polymerization reactor, purge with nitrogen three times, and heat to 150°C. Then keep it warm for 1 hour.

[0012] Preferably, in S2, the polymerization reaction specifically comprises: Heat to 240~260 Keep warm for 4-6 hours.

[0013] Preferably, in S3, the drying specifically involves: Between 100 and 130 Dry under a vacuum of 130 Pa for 4-8 hours.

[0014] The present invention also provides a nylon spinning masterbatch.

[0015] This invention also provides an application of nylon spinning masterbatch in nylon fabrics, wherein the nylon fabrics are made by blending nylon yarns with a mass ratio of 60-80%, and the nylon yarns are made by mixing the nylon spinning masterbatch with pure nylon 6 chips at a mass ratio of 10-30:70-90, and 230-250%. It is produced by melt blending and spinning.

[0016] Preferably, the nylon fabric further includes one or more of cotton fibers, spandex, or polyester.

[0017] Therefore, the present invention employs the above-mentioned nylon spinning masterbatch, its preparation method, and its application, and the beneficial effects are as follows: This invention regulates the degree of polymerization of nylon using acetic acid, and chemically bonds the nylon molecular chains through in-situ polymerization of nano-zinc oxide and tourmaline, resulting in uniform particle dispersion (no agglomeration or mutual interference). This ensures good blendability between the masterbatch and pure nylon chips. Utilizing the negative ion and far-infrared properties of tourmaline, the far-infrared thermal effect enhances the release efficiency of negative ions, while the far-infrared thermal effect synergistically inhibits bacteria growth in sweat with the antibacterial properties of zinc oxide, thus improving antibacterial activity and creating a synergistic effect of warmth, health, and hygiene. After 50 standard washes, the negative ion release of the nylon yarn still exceeds 400 ions / cm³. 3 It has a far-infrared emissivity greater than 0.85 and an inhibition rate of more than 95% against Escherichia coli and Staphylococcus aureus.

[0018] The masterbatch preparation process (in-situ polymerization), spinning process (melt blending), and weaving process of this invention are all compatible with existing nylon production lines, have low production costs, and are suitable for industrial production.

[0019] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0020] Figure 1 This is the infrared spectrum of a nylon spinning masterbatch, its preparation method, and an application example of the present invention; Figure 2 This is the UV-Vis absorption spectrum of a nylon spinning masterbatch, its preparation method, and its application example 1 of the present invention; Figure 3 This is a negative ion concentration-time curve of a nylon spinning masterbatch of the present invention, its preparation method, and application example two. Detailed Implementation

[0021] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0022] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0023] Example 1 A nylon spinning masterbatch is prepared by the following method: 1. Raw material pretreatment: After crushing the tourmaline, ball milling was performed for 2 hours, followed by sieving to obtain a particle size of 1~5 mm. m tourmaline powder.

[0024] Weigh 4.5g of nano zinc oxide (particle size 100nm), put it into a 1wt% silane coupling agent-ethanol solution, stir for 1h, sonicate in a constant temperature ultrasonic instrument at 60℃ for 10min, raise the temperature to 80℃, continue stirring until all the ethanol evaporates, and transfer to a 90℃ oven to dry for 2h to obtain nano zinc oxide antibacterial agent.

[0025] Weigh 90g of caprolactam and 10g of deionized water, 50 Stir and dissolve to obtain a 90% caprolactam aqueous solution.

[0026] 2. Raw material mixing: Add 22.5 g (25% of the caprolactam mass) of tourmaline powder, 4.5 g (5% of the caprolactam mass) of nano-zinc oxide antibacterial agent, and 0.45 mL (0.5% of the aqueous solution mass) of acetic acid to the above 90% caprolactam aqueous solution. Stir at 500 rpm for 30 minutes to form a uniformly dispersed mixture.

[0027] 3. In-situ polymerization: The mixture was transferred to a polymerization reactor, purged with nitrogen three times, and then heated to 150°C. Keep warm for 1 hour (prepolymerization); heat to 250°C The mixture was subjected to heat treatment polymerization for 5 hours (high temperature polymerization) to obtain nylon 6 chips.

[0028] 4. Post-processing: Nylon 6 chips were cooled to room temperature and cut into 2mm thick sheet-like coarse masterbatches. Soak in hot water for 4 hours, 120 The nylon spinning masterbatch was obtained by vacuum drying at 130 Pa for 6 hours (moisture content 0.08%, melt index 18 g / 10 min).

[0029] Example 2 A type of nylon yarn, the preparation method of which is as follows: The nylon spinning masterbatch obtained in Example 1 was mixed with pure nylon 6 chips at a mass ratio of 20:80, and then fed into a twin-screw extruder. Nitrogen gas was introduced, and the mixture was heated to 240°C. Melt blending, extrusion through a 0.3mm orifice spinneret, spinning at 3000m / min, 3.5 times draw, 120 The shape is set to produce nylon yarn.

[0030] Example 3 A nylon fabric, the preparation method of which is as follows: The nylon filament (70%) from Example 2 was blended with cotton fiber (25%) and spandex (5%), and woven on an air-jet loom at 350 rpm for 60 seconds. Desizing with hot water (containing 0.5% desizing enzyme), 80 Pre-shrinkage, 130 Shape and produce multifunctional underwear fabric.

[0031] Comparative Example 1 A nylon spinning masterbatch differs from Example 1 in that, in the raw material mixing step, 36g of tourmaline powder (40% of the mass of caprolactam) is added to a 90% caprolactam aqueous solution.

[0032] The obtained nylon spinning masterbatch was mixed with pure nylon 6 chips at a mass ratio of 20:80, and then fed into a twin-screw extruder at 240°C. Melt blending, nitrogen gas purging, extrusion through a 0.3mm orifice spinneret, spinning at 3000m / min, 3.5 times draw, 120 The shape is set to produce nylon yarn.

[0033] Comparative Example 2 A nylon spinning masterbatch is prepared by melt blending, and the preparation method is as follows: 1. Raw material mixing: Place pure nylon 6 chips (90 parts), tourmaline powder (25 parts), nano zinc oxide (3 parts), and random polypropylene (PP) compatibilizer (2 parts) in a high-speed mixer, 100 Stir for 10 minutes to obtain the premix; 2. Melt blending: The premixed material is added to a twin-screw extruder and melt-blended at 240°C. The mixture was melt-blended, extruded, and pelletized to obtain a tourmaline / nano zinc oxide / nylon composite masterbatch. 3. Nylon filament spinning: Tourmaline / nano zinc oxide / nylon composite masterbatch is mixed with pure nylon 6 chips at a ratio of 20:80, fed into a twin-screw extruder, and nitrogen is introduced at 240°C. Melt spinning, extruded through a 0.3mm orifice spinneret, spinning at 3000m / min, 3.5 times draw, 120 The shape is set to produce nylon yarn.

[0034] Test 1. The nylon spinning masterbatch prepared in Example 1 was characterized by infrared and ultraviolet-visible absorption spectroscopy. The results are as follows: Figures 1-2 As shown.

[0035] Depend on Figure 1 It can be known that 2900cm -1 The nearby multiplets represent the CH stretching vibration (methylene-CH2-), corresponding to the long-chain aliphatic hydrocarbon structure of nylon. (1630 cm⁻¹) -1 The strong peaks nearby are due to C=O stretching vibrations (amides). The band (a carbonyl peak) is a characteristic peak of the amide group. This indicates that nylon molecules were successfully polymerized.

[0036] Depend on Figure 2 It can be known that 667cm -1 and 791cm -1 The peak represents the Si-O-Si symmetric stretching vibration, formed by bond distortion. The band position depends on the Si-O-Si angle; as the bond angle increases, the band position rises. (1085 cm⁻¹) -1 The vibration at this point is an asymmetric stretching vibration of O—Si—O. 3441 cm⁻¹ -1 The characteristic spectral band of adsorbed water indicates that the tourmaline particles have surface adsorbed water or structural water after ball milling, indicating that the tourmaline powder has been successfully polymerized onto the nylon molecules.

[0037] 2. The nylon yarn prepared in Example 2 was subjected to functional testing. The testing method is as follows: Negative ion release was tested according to FZ / T 64045-2014, far-infrared emissivity according to GB / T 30127, and antibacterial performance according to GB / T 20944.2-2007. Washing treatment was performed, simulating 50 daily washes according to GB / T 8629-2017. The average values ​​of tensile strength and elongation at break were obtained from 10 nylon filaments according to GB / T 14344-2008.

[0038] The test results are as follows: like Figure 3 As shown, the average concentration of negative ions released by this nylon filament is 1546 ions / cm³. 3 Furthermore, even after 50 washes, the negative ion release rate is still greater than 400 ions / cm³. 3 .

[0039] The far-infrared emissivity of this nylon yarn is 0.88.

[0040] The nylon yarn exhibits an inhibition rate of 99.2% (unwashed) and 95.5% (50 washes) against Escherichia coli; and an inhibition rate of 99.5% (unwashed) and 96.1% (50 washes) against Staphylococcus aureus.

[0041] The nylon yarn has a tensile breaking strength of 4.5 cN / dtex and a breaking elongation of 30%.

[0042] 3. The performance of the nylon fabric in Example 3 was characterized. The test results showed that the air permeability of the nylon fabric was 180 mm / s, the color fastness to rubbing was ≥4, which met the Class A standard of GB 18401-2010, and there was no antibacterial agent migration.

[0043] 4. The nylon yarns prepared in Example 2 and Comparative Examples 1 to 2 were tested for negative ion release (unwashed and after 50 washes) and tensile breaking strength. The test results are shown in Table 1.

[0044] Table 1. Statistical Analysis of Test Results

[0045] As shown in Table 1, traditional melt blending is merely a physical mixing process, with no chemical bonding between the particles and the nylon matrix. Tourmaline and nano-zinc oxide are prone to agglomeration, resulting in low efficiency of the negative ion function. Furthermore, particle agglomeration disrupts the regularity of the nylon molecular chains, leading to a decrease in tensile strength. Excessive tourmaline exceeds the dispersion capacity of in-situ polymerization, and the excess particles cannot fully bond, resulting in agglomeration and disrupting the continuity of the nylon molecular chains, leading to a 37.8% reduction in tensile breaking strength. After washing, a large number of agglomerated particles detached, and the negative ion retention rate was only 29.1% of the initial level, far lower than the 55.2% in Example 2.

[0046] Therefore, the present invention adopts the above-mentioned nylon spinning masterbatch and its preparation method and application, which has synergistic effects of negative ions, far-infrared rays and antibacterial properties, and balanced performance, making it suitable for industrial production.

[0047] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A process for the preparation of a polyamide (nylon) spinning masterbatch, characterized in that, The method comprises the following steps: S1. In proportion, add tourmaline powder, antibacterial agent and acetic acid into 90% caprolactam aqueous solution in sequence, and stir to obtain uniformly dispersed mixture; S2, the mixture obtained in S1 is transferred to a polymerization kettle, heated to 140~160 , the prepolymerization is performed for 0.5~2h, and then the temperature is increased to perform polymerization, to obtain nylon 6 chips; S3, cooling the nylon 6 chips obtained in S2 to room temperature, cutting into sheet-like coarse master granules with a thickness of 2-3 mm, and placing in 75-85 hot water for leaching for 3-5 h, vacuum drying, to obtain polyamide spinning master granules.

2. The method for preparing a polyamide spinning master batch according to claim 1, characterized in that, In S1, the 90% caprolactam aqueous solution is specifically: Caprolactam and deionized water were mixed at a mass ratio of 9:1, 45~55 Stirring and dissolving, 90% caprolactam aqueous solution was prepared; The tourmaline powder is specifically: The tourmaline mineral is crushed, ball milled for 1.5-3 hours, sieved, and a particle size of 0.5-8 m of the tourmaline powder; The antibacterial agent is zinc oxide with a particle size of 50-200 nm, the zinc oxide is put into a 1wt% silane coupling agent-ethanol solution, stirred for 0.5-2 h, ultrasonically treated in a constant-temperature ultrasonic instrument at 55-65℃ for 5-15 min, heated to 75-80℃, and continuously stirred until the ethanol is completely volatilized, then moved into an oven at 85-90℃ for drying for at least 2 h.

3. The method for preparing a polyamide spinning master batch according to claim 2, characterized in that, In S1, the amount ratio of the caprolactam, the tourmaline powder, the zinc oxide and the acetic acid is 100g:25g:2-5g:0.5mL.

4. The method for preparing a polyamide spinning master batch according to claim 1, characterized in that, In S1, the stirring is specifically: at 45~55 at 500~800 r / min for 20~40 min.

5. The method for preparing a polyamide spinning master batch according to claim 1, characterized in that, In S2, the prepolymerization is specifically: The mixture was transferred into a polymerization kettle, replaced by nitrogen for 3 times, heated to 150 and then kept for 1 h.

6. The method for preparing a polyamide spinning master batch according to claim 1, characterized in that, In S2, the polymerization is specifically: Warming to 240~260 , and reaction for 4~6h.

7. The method for preparing a polyamide spinning masterbatch according to claim 1, characterized in that, In S3, the drying is specifically: at 100-130 under 130 Pa vacuum for 4-8 h.

8. A polyamide spinning master batch prepared by the method according to any one of claims 1-7.

9. Use of the polyamide spinning masterbatch according to claim 8 in polyamide fabrics, characterized in that: The nylon fabric is blended by 60-80% of nylon yarn by mass ratio, the nylon yarn is mixed by 10-30:70-90 of nylon spinning master batch and pure nylon 6 chip by mass ratio, 230-250 melt blending and spinning.

10. Use according to claim 9, characterized in that: The polyamide fabric further comprises one or more of cotton fiber, spandex or polyester. The polyamide fabric further comprises one or more of cotton fiber, spandex or polyester.

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