Research method of dope-dyed uvioresistant chinlon 66

Abstract

The invention discloses a research method of dope-dyed anti-ultraviolet chinlon 66. The research method comprises the following steps: coloring by an oxidation modification method; coloring by a coating modification method; coloring by a grafting modification method; and PA66 stock solution coloring CIELAB color brightness value comparison is carried out. According to the research method, the carbon black is subjected to surface treatment through oxidation modification, coating modification and grafting modification, and the influence of the modification method and process on the surface performance and the dispersing performance of the carbon black is researched; then, the modified carbon black is dispersed in a PA66 matrix through solvent volatilization, high-temperature and high-pressure solution prepolymerization-melting final polymerization and solid-phase polymerization, and the influence of carbon black particle surface modification and PA66 coloring modes on the compatibility and dispersity of the carbon black particles in the PA66 matrix is researched; the relationship between the mass fraction of the modified carbon black and the surface morphology, thermal performance, crystallization performance and CIELAB color brightness value of the PA66 film is explored. The high-quality nano carbon black is expected to be provided for coloring the PA66 fiber stock solution.

Description

Technical Field

[0001] The invention belongs to the technical field of anti-ultraviolet nylon, and specifically relates to a research method for solution-dyed anti-ultraviolet nylon 66. Background Art

[0002] Polyhexamethylene adipamide fiber is also known as polyamide 66 (PA66) fiber and nylon 66. It is one of the main varieties of aliphatic polyamide fibers. The resin is made from adipic acid and hexamethylenediamine, and then spun by melt spinning. The products are mainly filaments, but there are also deformed filaments and staple fibers. Fiber properties: melting point 255-264C. Glass transition temperature (Tg) 50C, density 1.14g / cm3. Ordinary fiber strength 4.9-5.6cN / dtex. Strong fiber is 5.7-7.7cN / dtcx. Elongation 26%-40%. Rebound rate is 95%-100% when elongated by 3%. Water absorption rate 4%. Soluble in meta-cresol. Can be made into woven, knitted, warp knitted fabrics, etc. Used for socks, underwear, shirts, sweatshirts, carpets, bedding decorative fabrics, etc. Can be blended with cotton, wool, viscose fibers, etc. In industry, it can be used to make tire cord, parachute silk, transmission belts, ropes, fishing nets, sewing threads and filter cloths, etc.

[0003] Polyhexamethylene adipamide (PA66) fibers are often dyed with weak acid dyes, but they have high crystallinity, low terminal amino content in the molecule, and weak interaction with dyes. Therefore, the dyed fibers have poor levelness, dyeing depth, and fastness. Solution dyeing refers to the processing technology of adding colorants to the PA66 polymerization process or spinning process to directly prepare colored fibers. It has the advantages of simple process, low cost, and low environmental pollution. It is a green and environmentally friendly fiber coloring technology. In recent years, there have been relatively more studies on solution dyeing of fibers such as polyester and viscose, and fewer studies on solution dyeing of PA66. Summary of the invention

[0004] (1) Technical issues to be solved

[0005] In view of the fact that there are few studies on the existing PA66 solution coloring, the purpose of the present invention is to provide a research method for solution-dyed UV-resistant nylon 66.

[0006] (2) Technical solution

[0007] In order to solve the above technical problems, the present invention provides a research method for solution-dyed UV-resistant nylon 66, comprising the following steps:

[0008] Oxidative modification coloring: Ammonium persulfate was used to oxidize carbon black in liquid phase to prepare oxidized carbon black (OCB), and OCB was used as a colorant to prepare PA66 film by solution blending method;

[0009] Coloring by coating modification method: PA66 salt-based carbon black dispersion was prepared by ultrasonic dispersion method, followed by self-dispersed carbon black (SPCB) prepared by spray drying method, and then PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization method. PA66 masterbatch was used as colorant and PA66 film was prepared by melt blending method;

[0010] Graft 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. Then, PA66 masterbatch was used as colorant and PA66 film was prepared by melt blending.

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

[0012] Preferably, ammonium persulfate is used to perform liquid phase oxidation on carbon black to prepare oxidized carbon black (OCB). Compared with the original carbon black, the O element content on the surface of OCB increases to 11.03%, and the OCB has good hydrophilicity and heat stability.

[0013] Furthermore, PA66 film was prepared by solution blending method with OCB as colorant. The study found that with the increase of OCB mass fraction, the average particle size of OCB increased, the melting temperature, crystallization temperature and crystallinity of the prepared PA66 film decreased, and the CIELAB color brightness value decreased.

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

[0015] Furthermore, self-dispersed carbon black (SPCB) was prepared by spray drying. The characteristic absorption peak of -CN, which is unique to polyvinyl pyrrolidone, appeared at a wave number of 1150cm-1 on the infrared spectrum curve (polyvinyl pyrrolidone itself does not directly contain a group such as -CN, but it is a high molecular compound formed by the polymerization of N-vinyl pyrrolidone monomer, which contains a -CN group with a molecular formula of (C6H9NO)n, where n represents the degree of polymerization), proving that polyvinyl pyrrolidone was successfully coated on the surface of carbon black; compared with the original carbon black, SPCB has excellent hydrophilicity and heat stability, and the average particle size after spontaneous dispersion in water is 202nm.

[0016] Furthermore, PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization, and PA66 film was prepared by melt blending with PA66 masterbatch as colorant. The study found that with the increase of SPCB mass fraction, SPCB was evenly 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 method, and OCB ethanol dispersion was prepared by ultrasonic dispersion method. The optimal preparation process was as follows: ammonium persulfate concentration was 1.5 mol / L, oxidation temperature was 60°C, and oxidation time was 4 h. Under these conditions, the average particle size of the OCB ethanol dispersion prepared was 151.7 nm, and the stability index was 76.5%.

[0018] Furthermore, OCB-PA66 salt was prepared by solution precipitation method, and PA66 masterbatch was prepared by solid phase polymerization method; compared with OCB, the average particle size of OCB-PA66 was about 200nm, the surface N element content reached 8.4%, and the 2θ value of X-ray diffraction showed characteristic diffraction peaks of PA66 at 20.5° and 23.5°, proving that PA66 molecular chains were grafted on the surface of OCB.

[0019] Furthermore, PA66 film was prepared by melt blending using PA66 masterbatch as colorant. The study found that with the increase of OCB mass fraction, the average particle size of OCB increased, the melting temperature, crystallization temperature and crystallinity of the PA66 film first decreased and then increased, and the CIELAB color brightness value decreased.

[0020] (3) Beneficial effects

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] The present invention performs surface treatment on carbon black by oxidation modification, coating modification and grafting modification respectively, and studies the influence of modification methods and processes on the surface properties and dispersion properties of carbon black; then disperses the modified carbon black in a PA66 matrix by solvent volatilization, high temperature and high pressure solution prepolymerization-melt final polymerization and solid phase polymerization respectively, studies the influence of surface modification of carbon black particles and PA66 coloring method on the compatibility and dispersion of carbon black particles in the PA66 matrix, explores the relationship between the mass fraction of modified carbon black and the surface morphology, thermal properties, crystallization properties and CIELAB color brightness value of PA66 film, in order to provide high-quality nano carbon black for PA66 fiber stock solution coloring.

[0023] Through experimental research, it was found that under the same mass fraction of carbon black, the CIELAB color brightness value of PA66 film colored by oxidation modification method was 58.10, the CIELAB color brightness value of PA66 film colored by coating modification method was 25.22, and the CIELAB color brightness value of PA66 film colored by grafting modification method was 26.03. According to experimental data, if PA66 film is used for applications requiring high transparency and clarity, the oxidation modification method will have a better coloring effect; if PA66 film is used for applications that require reduced light transmission or require specific color effects, the coating modification method will have a better coloring effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 A schematic diagram of the structure of a research method for a specific implementation of the device of the present invention;

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

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

[0027] Figure 4 This is a schematic diagram of the coloring structure of a grafting modification method of a specific implementation of the device of the present invention. DETAILED DESCRIPTION

[0028] This specific embodiment is a research method for solution-dyed UV-resistant nylon 66, and its structural schematic diagram is shown in FIG. Figure 1-4 As shown, the following steps are included:

[0029] Oxidative modification coloring: Ammonium persulfate was used to oxidize carbon black in liquid phase to prepare oxidized carbon black (OCB), and OCB was used as a colorant to prepare PA66 film by solution blending method;

[0030] Coloring by coating modification method: PA66 salt-based carbon black dispersion was prepared by ultrasonic dispersion method, followed by self-dispersed carbon black (SPCB) prepared by spray drying method, and then PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization method. PA66 masterbatch was used as colorant and PA66 film was prepared by melt blending method;

[0031] Graft 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. Then, PA66 masterbatch was used as colorant and PA66 film was prepared by melt blending.

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

[0033] Among them, ammonium persulfate was used to liquid-phase oxidize carbon black to prepare oxidized carbon black (OCB). Compared with the original carbon black, the O element content on the surface of OCB increased to 11.03%, and it had good hydrophilicity and heat stability. Using OCB as a colorant, PA66 film was prepared by solution blending method. The study found that with the increase of OCB mass fraction, the average particle size of OCB increased, the melting temperature, crystallization temperature and crystallinity of the prepared PA66 film decreased, and the CIELAB color brightness value decreased.

[0034] In specific use, when the OCB mass fraction is 0.2%, the particle size of larger carbon black agglomerates in the PA66 film is about 80μm, 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, a PA66-based carbon black dispersion was prepared by ultrasonic dispersion. The optimal preparation process was as follows: the mass fraction of polyvinyl pyrrolidone 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-based carbon black dispersion prepared was 184.1nm, the centrifugal stability was 96.20%, and the storage stability was 91.85%. Self-dispersed carbon black (SPCB) was prepared by spray drying. The characteristic absorption peak of -CN unique to polyvinyl pyrrolidone appeared on the infrared spectrum curve at a wave number of 1150cm-1 (polyvinyl pyrrolidone itself does not directly contain a group such as -CN, but it is through N-ethylene The polymer compound formed by the polymerization of polyvinyl pyrrolidone monomer contains -CN groups, and its molecular formula is (C6H9NO)n, where n represents the degree of polymerization), which proves that polyvinyl pyrrolidone is successfully coated on the surface of carbon black; compared with the original carbon black, SPCB has excellent hydrophilicity and heat 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, and PA66 film was prepared by melt blending with PA66 masterbatch as colorant. The study found that with the increase of SPCB mass fraction, SPCB is uniformly dispersed in the PA66 matrix, the melting temperature, crystallization temperature and crystallinity of the prepared PA66 film decrease, and the CIELAB color brightness value decreases.

[0036] In specific use, when the SPCB mass fraction is 0.2%, the average particle size of the carbon black particles in the PA66 film is about 200nm, 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] In addition, OCB was prepared by liquid phase oxidation method, and OCB ethanol dispersion was prepared by ultrasonic dispersion method. The optimal preparation process was ammonium persulfate concentration of 1.5 mol / L, oxidation temperature of 60°C, and oxidation time of 4 h. Under these conditions, the average particle size of OCB ethanol dispersion was 151.7 nm and the stability index was 76.5%. OCB-PA66 salt was prepared by solution precipitation method, and PA66 masterbatch was prepared by solid phase polymerization method. Compared with OCB, OCB-PA66 has an average The particle size is about 200nm, the surface N element content reaches 8.4%, and the 2θ value of X-ray diffraction shows characteristic diffraction peaks of PA66 at 20.5° and 23.5°, proving that the PA66 molecular chain is grafted on the OCB surface; PA66 masterbatch is used as a colorant, and the PA66 film is prepared by melt blending. The study found that with the increase of OCB mass fraction, the average particle size of OCB increases, the melting temperature, crystallization temperature and crystallinity of the PA66 film first decrease and then increase, and the CIELAB color brightness value decreases.

[0038] In specific use, when the OCB mass fraction is 0.2%, the average particle size of the carbon black particles in the PA66 film is about 200nm, 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 research method of this technical solution,

[0040] 1. Coloring by oxidation modification, the steps of which include: firstly, using ammonium persulfate to liquid-phase oxidize carbon black to prepare oxidized carbon black (OCB), and then using OCB as a colorant to prepare a PA66 film by a solution blending method;

[0041] 2. Coloring by coating modification method, the steps of which include: firstly preparing PA66 salt-based carbon black dispersion by ultrasonic dispersion method, then preparing self-dispersed carbon black (SPCB) by spray drying method, and the characteristic absorption peak of -CN unique to polyvinyl pyrrolidone appears on the infrared spectrum curve at the wave number of 1150cm-1 (polyvinyl pyrrolidone itself does not directly contain a group such as -CN, but it is a polymer compound obtained by polymerization of N-vinyl pyrrolidone monomer, which contains -CN group, and the molecular formula is (C6H9NO)n, wherein n represents the degree of polymerization), which proves that polyvinyl pyrrolidone is successfully coated on the surface of carbon black, and then preparing PA66 masterbatch by high temperature and high pressure melt prepolymerization-melt final polymerization method, and preparing PA66 film by melt blending method with PA66 masterbatch as colorant;

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

[0043] The PA66 films produced by the three preparation methods were compared. First, when the OCB mass fraction was 0.2%, the particle size of the larger carbon black agglomerates in the PA66 film was about 80μm, the melting temperature and crystallization temperature were 261.2℃ and 231.1℃ respectively, and the crystallinity was 18.6%; when the OCB mass fraction was 1.0%, the CIELAB color brightness value of the PA66 film was 58.10; then, when the SPCB mass fraction was 0.2%, the average particle size of the carbon black particles in the PA66 film was about 200nm, the melting temperature and crystallization temperature were The melting temperature and crystallization temperature of PA66 film were 259.2℃ and 230.8℃ respectively, and the crystallinity was 36.5%; when the SPCB mass fraction was 1.0%, the CIELAB color brightness value of PA66 film was 25.22; finally, when the OCB mass fraction was 0.2%, the average particle size of carbon black particles in PA66 film was about 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 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 preferred implementation schemes of the present invention. In addition, the present invention may also be implemented in other ways. Any obvious replacement without departing from the concept of the present technical solution is within the protection scope of the present invention.

Claims

1. A research method for solution-dyed UV-resistant nylon 66, characterized in that: The following steps are involved: Oxidative modification coloring: Ammonium persulfate was used to oxidize carbon black in liquid phase to prepare oxidized carbon black (OCB), and OCB was used as a colorant to prepare PA66 film by solution blending method; Coloring by coating modification method: PA66 salt-based carbon black dispersion was prepared by ultrasonic dispersion method, followed by self-dispersed carbon black (SPCB) prepared by spray drying method, and then PA66 masterbatch was prepared by high temperature and high pressure melt prepolymerization-melt final polymerization method. PA66 masterbatch was used as colorant and PA66 film was prepared by melt blending method; Graft 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. Then, PA66 masterbatch was used as colorant and PA66 film was prepared by melt blending. 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 were compared.

2. The research method of a solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that: Oxidized carbon black (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 surface of OCB increased to 11.03%, and it had good hydrophilicity and heat stability.

3. The research method of a solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that: PA66 film was prepared by solution blending method with OCB as colorant. The study found that with the increase of OCB mass fraction, the average particle size of OCB increased, the melting temperature, crystallization temperature and crystallinity of the prepared PA66 film decreased, and the CIELAB color brightness value decreased.

4. The research method of a solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that: PA66-based carbon black dispersion was prepared by ultrasonic dispersion. The optimal preparation process was as follows: the mass fraction of polyvinyl pyrrolidone 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-based carbon black dispersion prepared was 184.1nm, the centrifugal stability was 96.20%, and the placement stability was 91.85%.

5. The method for researching solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that: Self-dispersed carbon black (SPCB) was prepared by spray drying. The characteristic absorption peak of -CN, which is unique to polyvinyl pyrrolidone, appeared on the infrared spectrum curve at a wave number of 1150cm-1 (polyvinyl pyrrolidone itself does not directly contain a group such as -CN, but it is a high molecular compound formed by the polymerization of N-vinyl pyrrolidone monomer, which contains a -CN group with a molecular formula of (C6H9NO)n, where n represents the degree of polymerization), proving that polyvinyl pyrrolidone was successfully coated on the surface of carbon black; compared with the original carbon black, SPCB has excellent hydrophilicity and heat stability, and the average particle size is 202nm after spontaneous dispersion in water.

6. The method for developing 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 method, and PA66 film was prepared by melt blending method with PA66 masterbatch as colorant. The study found that with the increase of SPCB mass fraction, 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 developing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that: OCB was prepared by liquid phase oxidation method, and OCB ethanol dispersion was prepared by ultrasonic dispersion method. The optimal preparation process was as follows: ammonium persulfate concentration was 1.5 mol / L, oxidation temperature was 60°C, and oxidation time was 4 h. Under these conditions, the average particle size of OCB ethanol dispersion prepared was 151.7 nm, and the stability index was 76.5%.

8. The method for developing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that: OCB-PA66 salt was prepared by solution precipitation method, and PA66 masterbatch was prepared by solid phase polymerization method; compared with OCB, the average particle size of OCB-PA66 was about 200nm, the surface N element content reached 8.4%, and the 2θ value of X-ray diffraction showed characteristic diffraction peaks of PA66 at 20.5° and 23.5°, proving that PA66 molecular chains were grafted on the OCB surface.

9. The method for developing solution-dyed UV-resistant nylon 66 according to claim 1, characterized in that: PA66 film was prepared by melt blending with PA66 masterbatch as colorant. The study found that with the increase of OCB mass fraction, the average particle size of OCB increased, the melting temperature, crystallization temperature and crystallinity of PA66 film first decreased and then increased, and the CIELAB color brightness value decreased.

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