Preparation method of original solution colored anti-ultraviolet nylon 66

Abstract

The application discloses a preparation method of a stock solution colored anti-ultraviolet nylon 66, and comprises the following steps: oxidation modification coloring, coating modification coloring, graft modification coloring and PA66 stock solution colored CIELAB color brightness value comparison. The preparation method is characterized in that: carbon black is surface treated through oxidation modification, coating modification and graft modification respectively, the influence of modification methods and processes on the surface performance and dispersion performance of carbon black is researched; then, the modified carbon black is dispersed in a PA66 matrix through solvent evaporation, high-temperature and high-pressure solution pre-polymerization-melt final polymerization and solid-phase polymerization, the influence of carbon black particle surface modification and PA66 coloring methods on the compatibility and dispersion of carbon black particles in the PA66 matrix is researched, and the relationship among the mass fraction of modified carbon black, the surface morphology of the PA66 film, the thermal performance, the crystallization performance and the CIELAB color brightness value is explored. High-quality nano carbon black is provided for PA66 fiber stock solution coloring.

Description

Technical Field

[0001] This invention belongs to the field of UV-resistant nylon technology, specifically relating to a method for preparing solution-dyed UV-resistant nylon 66. Background Technology

[0002] Polyhexamethylene adipamide fiber, also known as polyamide 66 (PA66) fiber or nylon 66, is one of the main varieties of aliphatic polyamide fibers. It is produced by melt spinning of resin obtained from adipic acid and hexamethylenediamine. The main product is filament, but textured yarns and staple yarns are also available. Fiber properties: Melting point 255–264°C, glass transition temperature (Tg) 50°C, density 1.14 g / cm³. Ordinary fiber strength 4.9–5.6 cN / dtex. High-strength yarn 5.7–7.7 cN / dtcx. Elongation 26%–40%. Rebound rate 95%–100% at 3% elongation. Water absorption 4%. Soluble in m-cresol. It can be used to make woven, knitted, and warp-knitted fabrics. Applications include socks, underwear, shirts, sweatshirts, carpets, bedding fabrics, etc. It can be blended with cotton, wool, viscose fibers, etc. In industrial applications, it can be used to manufacture tire cords, parachute fabrics, transmission belts, ropes, fishing nets, sewing threads, and filter cloths, among other things.

[0003] Polyhexamethylene adipamide (PA66) fibers are commonly dyed with weakly acidic dyes. However, due to its high crystallinity, low content of terminal amino groups in the molecule, and weak interaction with dyes, the dyed fibers exhibit poor leveling properties, dyeing depth, and fastness. Solution dyeing refers to a processing technology that directly prepares colored fibers by adding colorants during the polymerization or spinning process of PA66. It boasts advantages such as simple process, low cost, and minimal environmental pollution, making it a green and environmentally friendly fiber dyeing technology. In recent years, there has been relatively more research on solution dyeing of polyester and viscose fibers, while research on PA66 solution dyeing is less extensive. Summary of the Invention

[0004] (1) Technical problems to be solved

[0005] Given the limited existing research on solution dyeing of PA66, the purpose of this invention is to provide a method for preparing solution-dyed UV-resistant nylon 66.

[0006] (2) Technical solution

[0007] To address the aforementioned technical problems, this invention provides a method for preparing solution-dyed UV-resistant nylon 66, comprising the following steps:

[0008] Oxidative modification coloring: Carbon black oxide (OCB) was prepared by liquid-phase oxidation of carbon black with ammonium persulfate. PA66 film was prepared by solution blending using OCB as a colorant.

[0009] Coloring by coating modification: PA66 basic carbon black dispersion was prepared by ultrasonic dispersion, then self-dispersible carbon black SPCB was prepared by spray drying, and then PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization. PA66 film was prepared by melt blending using PA66 masterbatch as colorant.

[0010] Grafting modification coloring: OCB was prepared by liquid phase oxidation and OCB ethanol dispersion was prepared by ultrasonic dispersion. Then, OCB-PA66 salt was prepared by solution precipitation and PA66 masterbatch was prepared by solid phase polymerization. Finally, PA66 film was prepared by melt blending using PA66 masterbatch as colorant.

[0011] Comparison of CIELAB color brightness values ​​of PA66 raw solution colored: The CIELAB color brightness values ​​of PA66 films colored by oxidation modification, coating modification and grafting modification are compared.

[0012] Preferably, carbon black oxide (OCB) is prepared by liquid-phase oxidation of carbon black using ammonium persulfate. Compared with the original carbon black, the O element content on the surface of OCB increases to 11.03%, exhibiting good hydrophilicity and heat resistance.

[0013] Furthermore, PA66 films were prepared by solution blending using OCB as a colorant. As the mass fraction of OCB increased, the average particle size of OCB increased, and the melting temperature, crystallization temperature, and crystallinity of the prepared PA66 films decreased, while the CIELAB color brightness value decreased.

[0014] Furthermore, a PA66 basic carbon black dispersion was prepared by ultrasonic dispersion. The preparation process involved a polyvinylpyrrolidone mass fraction of 15% to carbon black and a carbon black mass fraction of 10% to the system. The ultrasonic treatment power was 1260W and the time was 80min. Under these conditions, the PA66 basic carbon black dispersion had an average particle size of 184.1nm, a centrifugal stability of 96.20%, and a storage stability of 91.85%.

[0015] Furthermore, self-dispersible carbon black (SPCB) was prepared by spray drying, and its infrared spectrum showed a wavenumber of 1150 cm⁻¹. -1 The characteristic absorption peak of -CN, unique to polyvinylpyrrolidone, appeared at the point. Polyvinylpyrrolidone itself does not directly contain a group like -CN, but it is a polymer compound formed by the polymerization of N-vinylpyrrolidone monomers and does contain a -CN group. Its molecular formula is (C6H9NO)n, where n represents the degree of polymerization. This proves that polyvinylpyrrolidone was successfully coated on the carbon black surface. Compared with the original carbon black, SPCB has excellent hydrophilicity and heat resistance. After spontaneous dispersion in water, the average particle size is 202 nm.

[0016] Furthermore, PA66 masterbatch was prepared by high-temperature and high-pressure melt prepolymerization-melt final polymerization. Using PA66 masterbatch as a colorant, PA66 film was prepared by melt blending. As the mass fraction of SPCB increased, SPCB was uniformly dispersed in the PA66 matrix. The melting temperature, crystallization temperature, and crystallinity of the prepared PA66 film decreased, and the CIELAB color brightness value decreased.

[0017] Furthermore, OCB was prepared by liquid-phase oxidation and OCB ethanol dispersion was prepared by ultrasonic dispersion. The preparation process was as follows: ammonium persulfate concentration of 1.5 mol / L, oxidation temperature of 60℃, and oxidation time of 4 h. Under these conditions, the average particle size of the OCB ethanol dispersion was 151.7 nm and the stability index was 76.5%.

[0018] Furthermore, OCB-PA66 salt was prepared by solution precipitation and PA66 masterbatch was prepared by solid-state polymerization. Compared with OCB, OCB-PA66 has an average particle size of 200 nm and a surface nitrogen content of 8.4%. The characteristic diffraction peaks of PA66 were observed at 20.5° and 23.5° in X-ray diffraction, proving that PA66 molecules are linked to the OCB surface.

[0019] Furthermore, PA66 films were prepared by melt blending using PA66 masterbatch as a colorant. As the mass fraction of OCB increased, the average particle size of OCB increased, and the melting temperature, crystallization temperature, and crystallinity of the PA66 film first decreased and then increased, while the CIELAB color brightness value decreased.

[0020] (3) Beneficial effects

[0021] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] This invention involves surface treatment of carbon black through oxidation modification, coating modification, and grafting modification, respectively, and studies the effects of modification methods and processes on the surface and dispersion properties of carbon black. Subsequently, modified carbon black is dispersed in a PA66 matrix through solvent evaporation, high-temperature and high-pressure solution prepolymerization-melt final polymerization, and solid-state polymerization, respectively. The effects of carbon black particle surface modification and PA66 coloring methods on the compatibility and dispersibility of carbon black particles in the PA66 matrix are investigated. The relationship between the mass fraction of modified carbon black and the surface morphology, thermal properties, crystallinity, and CIELAB color brightness value of PA66 film is explored, with the aim of providing high-quality nano-carbon black for solution coloring of PA66 fibers.

[0023] Experiments showed that, with the same carbon black mass fraction, the CIELAB color brightness value of PA66 film colored by oxidation modification was 58.10, that of PA66 film colored by coating modification was 25.22, and that of PA66 film colored by grafting modification was 26.03. Based on the experimental data, if PA66 film is used in applications requiring high transparency and clarity, oxidation modification is more effective; if PA66 film is used in applications requiring reduced light transmission or specific color effects, coating modification is more effective. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the preparation method of a specific embodiment of the device of the present invention;

[0025] Figure 2 This is a schematic diagram of the coloring structure using the oxidation modification method in a specific embodiment of the device of the present invention;

[0026] Figure 3 This is a schematic diagram of the coloring structure using the coating modification method in a specific embodiment of the device of the present invention;

[0027] Figure 4 This is a schematic diagram of the grafting modification method coloring structure of a specific embodiment of the device of the present invention. Detailed Implementation

[0028] This specific embodiment is a method for preparing solution-dyed UV-resistant nylon 66, and its structural schematic diagram is shown below. Figure 1-4 As shown, it includes the following steps:

[0029] Oxidative modification coloring: Carbon black oxide (OCB) was prepared by liquid-phase oxidation of carbon black with ammonium persulfate. PA66 film was prepared by solution blending using OCB as a colorant.

[0030] Coloring by coating modification: PA66 basic carbon black dispersion was prepared by ultrasonic dispersion, then self-dispersible carbon black SPCB was prepared by spray drying, and then PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization. PA66 film was prepared by melt blending using PA66 masterbatch as colorant.

[0031] Grafting modification coloring: OCB was prepared by liquid phase oxidation and OCB ethanol dispersion was prepared by ultrasonic dispersion. Then, OCB-PA66 salt was prepared by solution precipitation and PA66 masterbatch was prepared by solid phase polymerization. Finally, PA66 film was prepared by melt blending using PA66 masterbatch as colorant.

[0032] Comparison of CIELAB color brightness values ​​of PA66 raw solution colored: The CIELAB color brightness values ​​of PA66 films colored by oxidation modification, coating modification and grafting modification are compared.

[0033] Among them, carbon black oxide (OCB) was prepared by liquid-phase oxidation of carbon black using ammonium persulfate. Compared with the original carbon black, the O element content on the OCB surface increased to 11.03%, exhibiting good hydrophilicity and heat resistance. PA66 film was prepared by solution blending using OCB as a colorant. As the mass fraction of OCB increased, the average particle size of OCB increased, while the melting temperature, crystallization temperature, and crystallinity of the prepared PA66 film decreased, and the CIELAB color brightness value decreased.

[0034] In practical applications, when the OCB mass fraction is 0.2%, the particle size of the larger carbon black agglomerates in the PA66 film is approximately 80 μm, the melting temperature and crystallization temperature are 261.2℃ and 231.1℃ respectively, and the crystallinity is 18.6%; when the OCB mass fraction is 1.0%, the CIELAB color brightness value of the PA66 film is 58.10.

[0035] In addition, PA66 basic carbon black dispersions were prepared by ultrasonic dispersion. The preparation process involved a polyvinylpyrrolidone mass fraction of 15% to carbon black and a carbon black mass fraction of 10% to the system. The ultrasonic treatment power was 1260W for 80 min. Under these conditions, the average particle size of the PA66 basic carbon black dispersion was 184.1 nm, the centrifugal stability was 96.20%, and the storage stability was 91.85%. Self-dispersible carbon black (SPCB) was prepared by spray drying. The infrared spectrum showed a value at a wavenumber of 1150 cm⁻¹. -1 The characteristic absorption peak of -CN, unique to polyvinylpyrrolidone, appeared. Polyvinylpyrrolidone itself does not directly contain a -CN group, but it is a polymer compound formed by the polymerization of N-vinylpyrrolidone monomers and does contain a -CN group, with the molecular formula (C6H9NO)n, where n represents the degree of polymerization. This proves that polyvinylpyrrolidone was successfully coated on the carbon black surface. Compared with the original carbon black, SPCB has excellent hydrophilicity and heat resistance stability, and the average particle size is 202nm after spontaneous dispersion in water. PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization method. PA66 film was prepared by melt blending using PA66 masterbatch as colorant. With the increase of SPCB mass fraction, SPCB is uniformly dispersed in PA66 matrix. The melting temperature, crystallization temperature and crystallinity of PA66 film decreased, and the CIELAB color brightness value decreased.

[0036] In practical applications, when the SPCB mass fraction is 0.2%, the average particle size of carbon black particles in the PA66 film is 200 nm, the melting temperature and crystallization temperature are 259.2℃ and 230.8℃ respectively, and the crystallinity is 36.5%; when the SPCB mass fraction is 1.0%, the CIELAB color brightness value of the PA66 film is 25.22.

[0037] Furthermore, OCB was prepared via liquid-phase oxidation, and an ethanol dispersion of OCB was prepared via ultrasonic dispersion. The preparation process involved an ammonium persulfate concentration of 1.5 mol / L, an oxidation temperature of 60℃, and an oxidation time of 4 h. Under these conditions, the average particle size of the OCB ethanol dispersion was 151.7 nm, and the stability index was 76.5%. OCB-PA66 salt was prepared via solution precipitation, and PA66 masterbatch was prepared via solid-phase polymerization. Compared with OCB, OCB-PA66 had an average particle size of 200 nm, a surface nitrogen content of 8.4%, and characteristic diffraction peaks of PA66 were observed at 20.5° and 23.5° in X-ray diffraction, indicating that PA66 molecules were linked to the OCB surface. Using PA66 masterbatch as a colorant, PA66 films were prepared via melt blending. With increasing OCB mass fraction, the average particle size of OCB increased, while the melting temperature, crystallization temperature, and crystallinity of the PA66 film first decreased and then increased, and the CIELAB color brightness value decreased.

[0038] In practical applications, when the OCB mass fraction is 0.2%, the average particle size of carbon black particles in the PA66 film is 200 nm, the melting temperature and crystallization temperature are 256.8℃ and 225.5℃ respectively, and the crystallinity is 31.5%; when the OCB mass fraction is 1.0%, the CIELAB color brightness value of the PA66 film is 26.03.

[0039] Working principle: When using the preparation method of this technical solution,

[0040] 1. Coloring is achieved by oxidation modification, the steps of which include: firstly, carbon black is oxidized by liquid phase oxidation with ammonium persulfate to prepare carbon black OCB, and then PA66 film is prepared by solution blending with OCB as a colorant.

[0041] 2. Coloring was achieved through a coating modification method, the steps of which included: firstly, a PA66 basic carbon black dispersion was prepared by ultrasonic dispersion, and then self-dispersible carbon black SPCB was prepared by spray drying. The infrared spectrum showed a wavenumber of 1150 cm⁻¹. -1The characteristic absorption peak of -CN, unique to polyvinylpyrrolidone, appeared. Polyvinylpyrrolidone itself does not directly contain a group like -CN, but it is a polymer compound formed by the polymerization of N-vinylpyrrolidone monomers and does contain a -CN group. Its molecular formula is (C6H9NO)n, where n represents the degree of polymerization. This proves that polyvinylpyrrolidone was successfully coated on the surface of carbon black. Then, PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization method. Using PA66 masterbatch as a colorant, PA66 film was prepared by melt blending method.

[0042] 3. Coloring is carried out by grafting modification, the steps of which include: firstly, OCB is prepared by liquid phase oxidation and OCB ethanol dispersion is prepared by ultrasonic dispersion; then, OCB-PA66 salt is prepared by solution precipitation and PA66 masterbatch is prepared by solid phase polymerization; then, PA66 film is prepared by melt blending using PA66 masterbatch as colorant.

[0043] A comparison was made of PA66 films produced by three different methods. First, when the OCB mass fraction was 0.2%, the particle size of the larger carbon black agglomerates in the PA66 film was approximately 80 μm, with melting and crystallization temperatures of 261.2℃ and 231.1℃, respectively, and a crystallinity of 18.6%. When the OCB mass fraction was 1.0%, the CIELAB color brightness value of the PA66 film was 58.10. Next, when the SPCB mass fraction was 0.2%, the average particle size of the carbon black particles in the PA66 film was 200 nm, with melting and crystallization temperatures of [missing information]. The crystallinity was 36.5% at temperatures of 259.2℃ and 230.8℃, respectively; when the SPCB mass fraction was 1.0%, the CIELAB color brightness value of the PA66 film was 25.22; finally, when the OCB mass fraction was 0.2%, the average particle size of the carbon black particles in the PA66 film was 200nm, the melting temperature and crystallization temperature were 256.8℃ and 225.5℃, respectively, and the crystallinity was 31.5%; when the OCB mass fraction was 1.0%, the CIELAB color brightness value of the PA66 film was 26.03.

[0044] All technical features in this embodiment can be freely combined according to actual needs.

[0045] The above embodiments are implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious substitutions without departing from the concept of the present technical solution are within the protection scope of the present invention.

Claims

1. A method for preparing solution-dyed UV-resistant nylon 66, characterized in that, Includes the following steps: Oxidative modification coloring: Carbon black oxide (OCB) was prepared by liquid-phase oxidation of carbon black with ammonium persulfate. PA66 film was prepared by solution blending using OCB as a colorant. Coloring by coating modification: PA66 basic carbon black dispersion was prepared by ultrasonic dispersion, then self-dispersible carbon black SPCB was prepared by spray drying, and then PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization. PA66 film was prepared by melt blending using PA66 masterbatch as colorant. Grafting modification coloring: OCB was prepared by liquid phase oxidation and OCB ethanol dispersion was prepared by ultrasonic dispersion. Then, OCB-PA66 salt was prepared by solution precipitation and PA66 masterbatch was prepared by solid phase polymerization. Finally, PA66 film was prepared by melt blending using PA66 masterbatch as colorant. Comparison of CIELAB color brightness values ​​of PA66: The CIELAB color brightness values ​​of PA66 films colored by oxidation modification, coating modification and grafting modification are compared.

2. The method for preparing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that, Carbon black oxide (OCB) was prepared by liquid-phase oxidation of carbon black with ammonium persulfate. Compared with the original carbon black, the O content on the surface of OCB increased to 11.03%, and it has good hydrophilicity and heat resistance.

3. The method for preparing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that, PA66 films were prepared by solution blending using OCB as a colorant. As the mass fraction of OCB increased, the average particle size of OCB increased, and the melting temperature, crystallization temperature, and crystallinity of the prepared PA66 films decreased, while the CIELAB color brightness value decreased.

4. The method for preparing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that, PA66 basic carbon black dispersion was prepared by ultrasonic dispersion. The preparation process was as follows: the mass fraction of polyvinylpyrrolidone to carbon black was 15%, the mass fraction of carbon black to the system was 10%, the ultrasonic treatment power was 1260W, and the time was 80min. Under these conditions, the average particle size of the PA66 basic carbon black dispersion was 184.1nm, the centrifugal stability was 96.20%, and the storage stability was 91.85%.

5. The method for preparing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that, Self-dispersed carbon black (SPCB) was prepared by spray drying. Its infrared spectrum showed a wavenumber of 1150 cm⁻¹. -1 The characteristic absorption peak of -CN, unique to polyvinylpyrrolidone, appeared. Polyvinylpyrrolidone itself does not directly contain a group like -CN, but it is a polymer compound formed by the polymerization of N-vinylpyrrolidone monomers and does contain a -CN group. Its molecular formula is (C6H9NO)n, where n represents the degree of polymerization. This proves that polyvinylpyrrolidone was successfully coated on the carbon black surface. Compared with the original carbon black, SPCB has excellent hydrophilicity and heat resistance. After spontaneous dispersion in water, the average particle size is 202 nm.

6. The method for preparing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that, PA66 masterbatch was prepared by high-temperature and high-pressure melt prepolymerization-melt final polymerization. PA66 film was prepared by melt blending using PA66 masterbatch as colorant. As the mass fraction of SPCB increased, SPCB was uniformly dispersed in the PA66 matrix. The melting temperature, crystallization temperature and crystallinity of the prepared PA66 film decreased, and the CIELAB color brightness value decreased.

7. The method for preparing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that, OCB was prepared by liquid-phase oxidation and then by ultrasonic dispersion. The preparation process involved an ammonium persulfate concentration of 1.5 mol / L, an oxidation temperature of 60 °C, and an oxidation time of 4 h. Under these conditions, the average particle size of the OCB ethanol dispersion was 151.7 nm and the stability index was 76.5%.

8. The method for preparing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that, OCB-PA66 salt was prepared by solution precipitation, and PA66 masterbatch was prepared by solid-state polymerization. Compared with OCB, OCB-PA66 has an average particle size of 200 nm and a surface nitrogen content of 8.4%. The characteristic diffraction peaks of PA66 were observed at 20.5° and 23.5° in X-ray diffraction, proving that PA66 molecules are linked to the OCB surface.

9. The method for preparing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that, PA66 films were prepared by melt blending using PA66 masterbatch as a colorant. As the mass fraction of OCB increased, the average particle size of OCB increased, and the melting temperature, crystallization temperature, and crystallinity of the PA66 film first decreased and then increased, while the CIELAB color brightness value decreased.

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