CN119265734B - Easily-dyed antioxidant nylon filament and preparation method thereof - Google Patents
Easily-dyed antioxidant nylon filament and preparation method thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
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Abstract
本发明提出了一种易染色抗氧化尼龙长丝及其制备方法，属于尼龙技术领域。将经过聚多巴胺包覆改性的多孔二氧化硅纳米球与硅烷偶联剂共聚3,5‑二叔丁基‑4‑羟基苯乙烯酸的抗氧剂偶联，表面包覆氧化石墨烯，加入己内酰胺中，加入氨基己酸，加热减压搅拌反应，排料冷却，干燥，切片，制得尼龙切片，经过熔融挤出、纺丝、冷却、上油、牵伸定型、卷绕，制得易染色抗氧化尼龙长丝。本发明易染色抗氧化尼龙66长丝纤维具有抗热氧老化性能好，易吸附色料分子，易染色，强度高、刚性好、抗冲击、耐油及耐化学品、耐磨和自润滑等优点，尤其是硬度、刚性、耐热性和蠕变性能更佳。The present invention proposes an easy-to-dye anti-oxidation nylon filament and a preparation method thereof, and belongs to the technical field of nylon. The porous silica nanospheres modified by polydopamine coating are coupled with an antioxidant of 3,5-di-tert-butyl-4-hydroxystyrene acid copolymerized with a silane coupling agent, the surface is coated with graphene oxide, added to caprolactam, aminocaproic acid is added, heated and decompressed, stirred and reacted, discharged and cooled, dried, sliced, and nylon slices are obtained, and after melt extrusion, spinning, cooling, oiling, drawing and shaping, and winding, easy-to-dye anti-oxidation nylon filaments are obtained. The easy-to-dye anti-oxidation nylon 66 filament fiber of the present invention has good resistance to thermal oxidation aging, easy adsorption of colorant molecules, easy dyeing, high strength, good rigidity, impact resistance, oil resistance and chemical resistance, wear resistance and self-lubrication, especially better hardness, rigidity, heat resistance and creep performance.
Description
Technical Field
The invention relates to the technical field of nylon, in particular to an easily-dyed antioxidant nylon filament and a preparation method thereof.
Background
The superfine fiber filament fabric is widely applied in the life of people at present, and is mainly applied to the fabrics of high-grade casual jackets, wind, casual western-style clothes, trousers, casual cotton-padded clothes and casual down jackets for men and women. The leather-like velvet fabric is generally manufactured by mainly adopting sea-island ultrafine fiber filaments or terylene-chinlon ultrafine fiber filaments, and is produced by the procedures of preshrinking, alkali deweighting, fiber opening, preshaping, napping, roughening, dyeing and the like. The nylon has the characteristics of molecular structure (containing amide groups and similar protein structure), good hydrophilic and skin-friendly properties, sweat absorption, light weight, good toughness, good rebound resilience, acid and alkali resistance and the like, is one of the artificial fabrics most suitable for human wearing, and is widely used in the fields of knitted underwear, hosiery, sportswear, skiing, tights and the like. The application of the nylon-6 fiber to clothing is one of the main applications of the nylon-6 fiber, and the micro-denier of the nylon-6 fiber can further improve the quality and the value of the fiber, so that high-grade clothing products which accord with the fashion trend and fashion taste can be manufactured. The single-filament number of the nylon 6 fiber obtained by the direct melt spinning method can reach 0.80dtex. A step of
However, the technology for directly producing the differential micro-denier nylon 6POY fiber by using the conventional spinning improvement method is not mature at present. The reason for the phenomenon is that on one hand, the sea-island spinning method is used for producing the differential micro-denier nylon, the process is complex, the cost is high, a large amount of organic matters are discharged and the environmental pollution is caused, the popularization and the application are obviously limited, and on the other hand, the molecular structure of the nylon contains a large amount of hydrogen bonds, the crystallization speed is high, the crystallization degree is high, and the nylon is not easy to stretch and deform.
Nylon materials are widely used for spinning, injection molding and film-forming products due to their unique performance advantages, but nylon is easy to oxidize and yellow, and finally causes the reduction of mechanical properties thereof to become a great disadvantage. The addition of a certain antioxidant in the molding process is a simple and commonly used method, but the effect cannot be optimally reflected due to the small addition amount and uneven dispersion of the antioxidant. The antioxidant master batch prepared by blending can alleviate the defect of uneven dispersion of the antioxidant to a certain extent, but the antioxidant master batch prepared by blending can cause certain thermal degradation, and has certain limitation to the fields with high requirements on the stability of nylon raw materials, such as high-speed fiber production. In addition, the specific surface area of the superfine denier nylon fiber is increased, the dyeing rate of the dye is increased, the leveling property is poor, and uneven dyeing is easy to occur.
Chinese patent CN1309899C is to dye the microfiber fiber of the fabric after chemical fiber opening and mechanical opening. The suede fabric is made of polyester sea-island fibers, polyester-nylon superfine fibers and other fibers, and the fineness of the fibers after splitting is about 0.2 dtex. The specific surface area of the fiber reaches tens of times of that of the conventional fiber, so that the adsorption capacity of the surface of the fiber is greatly enhanced when the disperse dye is dyed. Some dyes are combined with the fibers for dyeing, and 1/4-1/3 of the dyes are adsorbed on the surfaces of the fibers, so that sewage is often introduced during fabric cleaning, COD (chemical oxygen demand) emission is increased, and environmental pollution is caused.
Disclosure of Invention
The invention aims to provide an easily-dyed antioxidant nylon filament and a preparation method thereof, and the easily-dyed antioxidant nylon filament has the advantages of good thermal-oxidative aging resistance, easiness in adsorbing pigment molecules, easiness in dyeing, high strength, good rigidity, shock resistance, oil resistance, chemical resistance, wear resistance, self-lubrication and the like, and particularly has better hardness, rigidity, heat resistance and creep property.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of an easily-dyed antioxidant nylon filament, which comprises the steps of coupling a porous silica nanosphere subjected to polydopamine coating modification with an antioxidant of silane coupling agent copolymerized 3, 5-di-tert-butyl-4-hydroxystyroic acid, coating graphene oxide on the surface, adding caprolactam, adding aminocaproic acid, heating, decompressing, stirring for reaction, discharging, cooling, drying, slicing to obtain a nylon slice, and carrying out melt extrusion, spinning, cooling, oiling, drafting setting and winding to obtain the easily-dyed antioxidant nylon filament.
As a further improvement of the invention, the method comprises the following steps:
S1, dissolving alkyl orthosilicate in an organic solvent to obtain a solution A, dissolving a pore-forming agent and an emulsifying agent in water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying, regulating the pH value of the solution, stirring for reaction, centrifuging, washing and drying to obtain porous silica nanospheres;
S2, adding the porous silica nanospheres into water, adding dopamine hydrochloride and a catalyst, heating, stirring, reacting, centrifuging, washing and drying to obtain modified porous silica nanospheres;
s3, adding 3, 5-di-tert-butyl-4-hydroxystyric acid into ethanol, adding a silane coupling agent with double bonds and an initiator, heating, stirring, reacting, filtering, washing and drying to obtain an antioxidant;
S4, adding an antioxidant into water, adding NHS (N-Hydroxy succinimide ) and EDC (1- (3-Dimethylaminopropyl) -3-ethylcarbodiimide, 1-ethyl- (3-dimethylaminopropyl) carbodiimide), stirring for activation, adding modified porous silica nanospheres, stirring for reaction, centrifuging, washing and drying to obtain a conjugate;
S5, adding the conjugate into the graphene oxide aqueous dispersion, uniformly dispersing by ultrasonic, and spray-drying to obtain a fold-type coating modifier;
s6, heating and melting caprolactam, adding aminocaproic acid and a fold type coating modifier, stirring and mixing uniformly, heating, decompressing and stirring for reaction, discharging, cooling, drying and slicing to obtain nylon slices;
S7, conveying the nylon chips into a screw extruder, pressurizing and conveying the melt to a spinning box body, metering the melt by a metering pump, spraying the melt by a spinning component, cooling the filaments by side blowing to form filament bundles, oiling the cooled filament bundles to eliminate static electricity, carrying out drafting shaping treatment on the oiled filament bundles, and winding the shaped filament bundles into filament cylinders to obtain the easy-dyeing antioxidant nylon filaments.
As a further improvement of the invention, the alkyl orthosilicate in the step S1 is methyl orthosilicate or ethyl orthosilicate, the mass ratio of the alkyl orthosilicate to the pore-forming agent to the emulsifier is 12-15:1-2:0.5-1, the pore-forming agent is at least one of cetyltrimethylammonium chloride, ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20 or ethylene oxide-propylene oxide triblock copolymer PEO106-PPO70-PEO106, the emulsifier is at least one of tween-20, tween-40, tween-60, tween-80 or tween-85, the pH value of the solution is adjusted to be 9-10, and the stirring reaction time is 10-12h.
As a further improvement of the invention, in the step S2, the mass ratio of the porous silica nanospheres to the dopamine hydrochloride to the catalyst is 10-12:4-6:1-2, the catalyst is Tris-HCl solution with pH=8.5-9.5, the temperature of the heating and stirring reaction is 45-55 ℃ and the time is 3-5h.
As a further improvement of the invention, in the step S3, the mass ratio of the 3, 5-di-tert-butyl-4-hydroxystyronic acid to the silane coupling agent with double bonds to the initiator is 4-7:3-5:0.01-0.02, the silane coupling agent with double bonds is selected from at least one of KH570, A151 and A171, the initiator is azodiisobutyronitrile, the temperature of the heating and stirring reaction is 50-60 ℃, and the time is 3-5h.
As a further improvement of the invention, the mass ratio of the antioxidant, NHS, EDC and the modified porous silica nanospheres in the step S4 is 4-7:1-2:1-2:10, the stirring and activating time is 20-30min, and the stirring and reacting time is 8-10h.
As a further improvement of the invention, the concentration of the graphene oxide aqueous dispersion liquid in the step S5 is 0.5-1mg/mL, and the liquid-solid ratio of the graphene oxide aqueous dispersion liquid to the conjugate is 3-5 mL/1 g.
As a further improvement of the invention, the heating and melting temperature in the step S6 is 70-75 ℃, the mass ratio of the caprolactam to the aminocaproic acid to the fold coating modifier is 100:1-2:7-12, the heating, decompressing and stirring reaction temperature is 240-260 ℃, the rotating speed is 100-150r/min, the reaction pressure is 0.02-0.08MPa, and the time is 3-5h.
As a further improvement of the invention, the temperature of the melt extrusion in the step S7 is 280-300 ℃, the fineness of the filaments sprayed by the spinning is 0.05-0.1mm, the oil addition is controlled to be 0.5-1.5%, the drafting shaping is realized by 1-stage preheating, 2-stage stretching and 2-stage shaping between six pairs of hot rolls, wherein the temperature of the 1 st pair of hot rolls is 30-40 ℃, the temperature of the 2 nd pair of hot rolls is 45-55 ℃, the 1 st pair of hot rolls and the 2 nd pair of hot rolls play a role in preheating the filaments, the stretching ratio is 1-1.01 times, and the winding speed is 3000-4000m/min.
The invention further protects the easy-dyeing oxidation-resistant nylon filament prepared by the preparation method.
The invention has the following beneficial effects:
According to the invention, 3, 5-di-tert-butyl-4-hydroxystyric acid and a silane coupling agent with double bonds are copolymerized to prepare the antioxidant, on one hand, the antioxidant has a silane structure and can be well combined with silica nanospheres, and on the other hand, the macromolecular antioxidant containing polar groups, rigid five-membered rings and long-chain alkyl para-substituents in the molecular structure is prepared by adopting a free radical polymerization method, so that the macromolecular antioxidant with large relative molecular mass, good heat resistance and high heat-oxidation aging resistance efficiency can be prepared, the heat-oxidation aging resistance of nylon can be obviously improved, the dispersibility is good, the mechanical property of nylon filaments is not reduced, and the antioxidant is not easy to decompose. In addition, the antioxidant macromolecule is provided with rich carboxyl groups, the carboxyl groups can be coupled with amino groups on the modified porous silica nanospheres through activation, so that a conjugate is formed, the conjugate is added into nylon, the mechanical strength of nylon wires can be obviously improved, and due to the characteristic of large specific surface area of the porous silica nanospheres, pigment molecules are easy to adsorb, and the polydopamine coated on the porous silica nanospheres can form complex bonds or hydrogen bonds with metal ions and pigment molecules, so that the dye has a good color fixing effect and is easy to dye.
Graphene oxide and nylon have good compatibility, but the mechanical properties of nylon are affected by the easy agglomeration of the graphene oxide are directly added, the graphene oxide is coated on the surface of a conjugate and is subjected to spray drying to form folds, so that the uniform dispersion of the nano fold type coating modifier is realized, the formation of a heat conducting network is promoted by effective contact, the heat conductivity of the nano fold type coating modifier is improved, the promoted dispersibility and compatibility of the fold type coating modifier in a nylon material are improved, the graphene oxide is difficult to agglomerate, the mechanical properties and heat dissipation performance of the material are improved, and the heat shrinkage rate is reduced.
The easy-to-dye antioxidant nylon 66 filament fiber has the advantages of good thermal-oxidative aging resistance, easy adsorption of pigment molecules, easy dyeing, high strength, good rigidity, shock resistance, oil resistance, chemical resistance, wear resistance, self lubrication and the like, and particularly has better hardness, rigidity, heat resistance and creep property.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
0.5Mg/mL graphene oxide aqueous dispersion purchased from Jiangsu Xianfeng nanomaterial technologies Co.
Example 1
The embodiment provides a preparation method of an easily-dyed antioxidant nylon filament, which comprises the following steps:
S1, dissolving 12g of methyl orthosilicate in 200mL of dichloromethane to obtain a solution A, dissolving 1g of cetyltrimethylammonium chloride and 0.5g of tween-40 in 300mL of water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying for 15min at 7000r/min, regulating the pH value of the solution to 9, stirring and reacting for 10h, centrifuging, washing and drying to obtain the porous silicon dioxide nanospheres;
S2, adding 10g of porous silica nanospheres into 200mL of water, adding 4g of dopamine hydrochloride and 1g of catalyst, heating to 45 ℃, stirring for reaction for 3 hours, centrifuging, washing and drying to obtain modified porous silica nanospheres;
The catalyst is Tris-HCl solution with pH=8.5;
s3, adding 4g of 3, 5-di-tert-butyl-4-hydroxystyric acid into 200mL of ethanol, adding 3g of silane coupling agent A151 and 0.01g of azodiisobutyronitrile, heating to 50 ℃, stirring and reacting for 3h, filtering, washing and drying to obtain an antioxidant;
s4, adding 4g of antioxidant into 200mL of water, adding 1g of NHS and 1g of EDC, stirring and activating for 20min, adding 10g of modified porous silica nanospheres, stirring and reacting for 8h, centrifuging, washing and drying to obtain a conjugate;
s5, adding 10g of conjugate into 30mL of graphene oxide aqueous dispersion liquid with the concentration of 0.5mg/mL, performing 1000W ultrasonic dispersion for 10min, and performing spray drying to obtain a fold type coating modifier;
S6, heating 100g of caprolactam to 75 ℃ for melting, adding 1g of aminocaproic acid and 7g of fold type coating modifier, stirring and mixing for 15min, heating, decompressing and stirring for reaction at 240 ℃ at the speed of 100r/min under the pressure of 0.02MPa for 3h, discharging, cooling, drying and slicing to obtain nylon slices;
S7, conveying nylon chips into a screw extruder, heating to 280 ℃ to obtain a melt, pressurizing and conveying the melt to a spinning box, metering the melt by a metering pump, spraying the melt through a spinning component, wherein the fineness of the sprayed filaments is 0.1mm, cooling the filaments by side blowing to form filament bundles, eliminating static electricity by oiling the cooled filament bundles, controlling the attached quantity of the oil to be 0.5%, carrying out drafting shaping treatment on the oiled filament bundles, and carrying out 2-stage stretching and 2-stage shaping, wherein the temperature of the 1 st pair of hot rolls is 30 ℃, the temperature of the 2 nd pair of hot rolls is 45 ℃, the 1 st pair of hot rolls and the 2 nd pair of hot rolls play a role in preheating the filament bundles, the stretching ratio is 1 time, winding the shaped filament bundles into filament cylinders, and the winding speed is 3000m/min, so that the nylon filaments easy to dye and resist oxidation are obtained.
Example 2
The embodiment provides a preparation method of an easily-dyed antioxidant nylon filament, which comprises the following steps:
S1, dissolving 15g of ethyl orthosilicate in 200mL of dichloromethane to obtain a solution A, dissolving 2g of ethylene oxide-propylene oxide triblock copolymer PEO106-PPO70-PEO106 and 1g of tween-60 in 300mL of water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying for 15min at 7000r/min, adjusting the pH value of the solution to 10, stirring and reacting for 12h, centrifuging, washing and drying to obtain the porous silica nanospheres;
S2, adding 12g of porous silica nanospheres into 200mL of water, adding 6g of dopamine hydrochloride and 2g of catalyst, heating to 55 ℃, stirring and reacting for 5 hours, centrifuging, washing and drying to obtain modified porous silica nanospheres;
the catalyst is Tris-HCl solution with pH=9.5;
S3, adding 7g of 3, 5-di-tert-butyl-4-hydroxystyric acid into 200mL of ethanol, adding 5g of silane coupling agent A171 and 0.02g of azodiisobutyronitrile, heating to 60 ℃, stirring and reacting for 5h, filtering, washing and drying to obtain an antioxidant;
S4, adding 7g of antioxidant into 200mL of water, adding 2g of NHS and 2g of EDC, stirring and activating for 30min, adding 10g of modified porous silica nanospheres, stirring and reacting for 10h, centrifuging, washing and drying to obtain a conjugate;
S5, adding 10g of conjugate into 50mL of graphene oxide aqueous dispersion liquid with the concentration of 0.5mg/mL, performing 1000W ultrasonic dispersion for 10min, and performing spray drying to obtain a fold type coating modifier;
S6, heating 100g of caprolactam to 75 ℃ for melting, adding 2g of aminocaproic acid and 12g of fold type coating modifier, stirring and mixing for 15min, heating, decompressing and stirring for reaction at 260 ℃ at the speed of 150r/min and at the reaction pressure of 0.08MPa for 5h, discharging, cooling, drying and slicing to obtain nylon slices;
S7, conveying nylon chips into a screw extruder, heating to 300 ℃ to obtain a melt, pressurizing and conveying the melt to a spinning box, metering the melt by a metering pump, spraying the melt through a spinning component, wherein the fineness of the sprayed filaments is 0.1mm, cooling the filaments by side blowing to form filament bundles, eliminating static electricity by oiling the cooled filament bundles, controlling the attached quantity of the oil to be 1.5%, carrying out drafting shaping treatment on the oiled filament bundles, and carrying out 2-stage stretching and 2-stage shaping, wherein the temperature of the 1 st pair of hot rolls is 40 ℃, the temperature of the 2 nd pair of hot rolls is 55 ℃, the preheating effect of the 1 st pair of hot rolls and the 2 nd pair of hot rolls on the filament bundles is 1.01 times, and winding the shaped filament bundles into filament cylinders, and the winding speed is 4000m/min to obtain the easy-dyeing oxidation resistant nylon filaments.
Example 3
The embodiment provides a preparation method of an easily-dyed antioxidant nylon filament, which comprises the following steps:
S1, dissolving 13g of ethyl orthosilicate in 200mL of dichloromethane to obtain a solution A, dissolving 1.5g of an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and 0.8g of Tween-85 in 300mL of water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying for 15min at 7000r/min, adjusting the pH value of the solution to 9.5, stirring and reacting for 11h, centrifuging, washing and drying to obtain the porous silica nanospheres;
s2, adding 11g of porous silica nanospheres into 200mL of water, adding 5g of dopamine hydrochloride and 1.5g of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, centrifuging, washing and drying to obtain modified porous silica nanospheres;
the catalyst is Tris-HCl solution with pH=9;
S3, adding 5.5g of 3, 5-di-tert-butyl-4-hydroxystyric acid into 200mL of ethanol, adding 4g of silane coupling agent KH570 and 0.015g of azodiisobutyronitrile, heating to 55 ℃, stirring and reacting for 4 hours, filtering, washing and drying to obtain an antioxidant;
s4, adding 5g of antioxidant into 200mL of water, adding 1.5g of NHS and 1.2g of EDC, stirring and activating for 25min, adding 10g of modified porous silica nanospheres, stirring and reacting for 9h, centrifuging, washing and drying to obtain a conjugate;
S5, adding 10g of conjugate into 40mL of 0.5mg/mL graphene oxide aqueous dispersion, performing 1000W ultrasonic dispersion for 10min, and performing spray drying to obtain a fold-type coating modifier;
S6, heating 100g of caprolactam to 75 ℃ for melting, adding 1.5g of aminocaproic acid and 10g of fold type coating modifier, stirring and mixing for 15min, heating, decompressing and stirring for reaction at 250 ℃ at the speed of 120r/min under the pressure of 0.05MPa for 4h, discharging, cooling, drying and slicing to obtain nylon slices;
S7, conveying nylon chips into a screw extruder, heating to 290 ℃ to obtain a melt, pressurizing and conveying the melt to a spinning box, metering the melt by a metering pump, spraying the melt through a spinning component, wherein the fineness of the sprayed filaments is 0.1mm, cooling the filaments by side blowing to form filament bundles, eliminating static electricity by oiling the cooled filament bundles, controlling the attached quantity of the oil to be 1%, carrying out drafting shaping treatment on the oiled filament bundles, and carrying out 2-stage stretching and 2-stage shaping on the drafting shaping filament bundles, wherein the temperature of the 1 st pair of hot rolls is 35 ℃, the temperature of the 2 nd pair of hot rolls is 50 ℃, the 1 st pair of hot rolls and the 2 nd pair of hot rolls are used for preheating the filament bundles, the stretching ratio is 1 time, and winding the shaped filament bundles into filament cylinders, and the winding speed is 3500m/min, so that the dyeing-easy oxidation resistant nylon filament is prepared.
Comparative example 1
The difference compared to example 3 is that no Kong Jiyang ethylene-propylene oxide triblock copolymer PEO20-PPO70-PEO20 was added in step S1.
The method comprises the following steps:
S1, dissolving 13g of ethyl orthosilicate in 200mL of dichloromethane to obtain a solution A, dissolving 2.3g of tween-85 in 300mL of water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying for 15min at 7000r/min, adjusting the pH value of the solution to 9.5, stirring and reacting for 11h, centrifuging, washing and drying to obtain the porous silicon dioxide nanospheres.
Comparative example 2
In comparison with example 3, the difference is that step S2 is not performed.
The method comprises the following steps:
S1, dissolving 13g of ethyl orthosilicate in 200mL of dichloromethane to obtain a solution A, dissolving 1.5g of an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and 0.8g of Tween-85 in 300mL of water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying for 15min at 7000r/min, adjusting the pH value of the solution to 9.5, stirring and reacting for 11h, centrifuging, washing and drying to obtain the porous silica nanospheres;
S2, adding 5.5g of 3, 5-di-tert-butyl-4-hydroxystyric acid into 200mL of ethanol, adding 4g of silane coupling agent KH570 and 0.015g of azodiisobutyronitrile, heating to 55 ℃, stirring and reacting for 4 hours, filtering, washing and drying to obtain an antioxidant;
S3, adding 5g of antioxidant into 200mL of water, adding 1.5g of NHS and 1.2g of EDC, stirring and activating for 25min, adding 10g of porous silica nanospheres, stirring and reacting for 9h, centrifuging, washing and drying to obtain a conjugate;
s4, adding 10g of conjugate into 40mL of graphene oxide aqueous dispersion, performing 1000W ultrasonic dispersion for 10min, and performing spray drying to obtain a fold type coating modifier;
s5, heating 100g of caprolactam to 75 ℃ for melting, adding 1.5g of aminocaproic acid and 10g of fold type coating modifier, stirring and mixing for 15min, heating, decompressing and stirring for reaction at 250 ℃ at the speed of 120r/min under the pressure of 0.05MPa for 4h, discharging, cooling, drying and slicing to obtain nylon slices;
S6, conveying nylon chips into a screw extruder, heating to 290 ℃ to obtain a melt, pressurizing and conveying the melt to a spinning box, metering the melt by a metering pump, spraying the melt through a spinning component, wherein the fineness of the sprayed filaments is 0.1mm, cooling the filaments by side blowing to form filament bundles, eliminating static electricity by oiling the cooled filament bundles, controlling the attached quantity of the oil to be 1%, carrying out drafting shaping treatment on the oiled filament bundles, and carrying out 2-stage stretching and 2-stage shaping on the drafting shaping filament bundles, wherein the temperature of the 1 st pair of hot rolls is 35 ℃, the temperature of the 2 nd pair of hot rolls is 50 ℃, the 1 st pair of hot rolls and the 2 nd pair of hot rolls are used for preheating the filament bundles, the stretching ratio is 1 time, and winding the shaped filament bundles into filament cylinders, and the winding speed is 3500m/min, so that the dyeing-easy oxidation resistant nylon filament is prepared.
Comparative example 3
In comparison with example 3, the process is different in that step S3 is not carried out, and the antioxidant in step S4 is 3, 5-di-tert-butyl-4-hydroxystyric acid.
The method comprises the following steps:
S1, dissolving 13g of ethyl orthosilicate in 200mL of dichloromethane to obtain a solution A, dissolving 1.5g of an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and 0.8g of Tween-85 in 300mL of water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying for 15min at 7000r/min, adjusting the pH value of the solution to 9.5, stirring and reacting for 11h, centrifuging, washing and drying to obtain the porous silica nanospheres;
s2, adding 11g of porous silica nanospheres into 200mL of water, adding 5g of dopamine hydrochloride and 1.5g of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, centrifuging, washing and drying to obtain modified porous silica nanospheres;
the catalyst is Tris-HCl solution with pH=9;
S3, adding 5g of 3, 5-di-tert-butyl-4-hydroxystyric acid into 200mL of water, adding 1.5g of NHS and 1.2g of EDC, stirring and activating for 25min, adding 10g of modified porous silica nanospheres, stirring and reacting for 9h, centrifuging, washing and drying to obtain a conjugate;
s4, adding 10g of conjugate into 40mL of graphene oxide aqueous dispersion, performing 1000W ultrasonic dispersion for 10min, and performing spray drying to obtain a fold type coating modifier;
s5, heating 100g of caprolactam to 75 ℃ for melting, adding 1.5g of aminocaproic acid and 10g of fold type coating modifier, stirring and mixing for 15min, heating, decompressing and stirring for reaction at 250 ℃ at the speed of 120r/min under the pressure of 0.05MPa for 4h, discharging, cooling, drying and slicing to obtain nylon slices;
S6, conveying nylon chips into a screw extruder, heating to 290 ℃ to obtain a melt, pressurizing and conveying the melt to a spinning box, metering the melt by a metering pump, spraying the melt through a spinning component, wherein the fineness of the sprayed filaments is 0.1mm, cooling the filaments by side blowing to form filament bundles, eliminating static electricity by oiling the cooled filament bundles, controlling the attached quantity of the oil to be 1%, carrying out drafting shaping treatment on the oiled filament bundles, and carrying out 2-stage stretching and 2-stage shaping on the drafting shaping filament bundles, wherein the temperature of the 1 st pair of hot rolls is 35 ℃, the temperature of the 2 nd pair of hot rolls is 50 ℃, the 1 st pair of hot rolls and the 2 nd pair of hot rolls are used for preheating the filament bundles, the stretching ratio is 1 time, and winding the shaped filament bundles into filament cylinders, and the winding speed is 3500m/min, so that the dyeing-easy oxidation resistant nylon filament is prepared.
Comparative example 4
In comparison with example 3, the difference is that step S5 is not performed.
The method comprises the following steps:
S1, dissolving 13g of ethyl orthosilicate in 200mL of dichloromethane to obtain a solution A, dissolving 1.5g of an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and 0.8g of Tween-85 in 300mL of water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying for 15min at 7000r/min, adjusting the pH value of the solution to 9.5, stirring and reacting for 11h, centrifuging, washing and drying to obtain the porous silica nanospheres;
s2, adding 11g of porous silica nanospheres into 200mL of water, adding 5g of dopamine hydrochloride and 1.5g of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, centrifuging, washing and drying to obtain modified porous silica nanospheres;
the catalyst is Tris-HCl solution with pH=9;
S3, adding 5.5g of 3, 5-di-tert-butyl-4-hydroxystyric acid into 200mL of ethanol, adding 4g of silane coupling agent KH570 and 0.015g of azodiisobutyronitrile, heating to 55 ℃, stirring and reacting for 4 hours, filtering, washing and drying to obtain an antioxidant;
s4, adding 5g of antioxidant into 200mL of water, adding 1.5g of NHS and 1.2g of EDC, stirring and activating for 25min, adding 10g of modified porous silica nanospheres, stirring and reacting for 9h, centrifuging, washing and drying to obtain a conjugate;
s5, heating 100g of caprolactam to 75 ℃ for melting, adding 1.5g of aminocaproic acid and 10g of conjugate, stirring and mixing for 15min, heating, decompressing and stirring for reaction, wherein the temperature is 250 ℃, the rotating speed is 120r/min, the reaction pressure is 0.05MPa, the time is 4h, discharging, cooling, drying and slicing to obtain nylon slices;
S6, conveying nylon chips into a screw extruder, heating to 290 ℃ to obtain a melt, pressurizing and conveying the melt to a spinning box, metering the melt by a metering pump, spraying the melt through a spinning component, wherein the fineness of the sprayed filaments is 0.1mm, cooling the filaments by side blowing to form filament bundles, eliminating static electricity by oiling the cooled filament bundles, controlling the attached quantity of the oil to be 1%, carrying out drafting shaping treatment on the oiled filament bundles, and carrying out 2-stage stretching and 2-stage shaping on the drafting shaping filament bundles, wherein the temperature of the 1 st pair of hot rolls is 35 ℃, the temperature of the 2 nd pair of hot rolls is 50 ℃, the 1 st pair of hot rolls and the 2 nd pair of hot rolls are used for preheating the filament bundles, the stretching ratio is 1 time, and winding the shaped filament bundles into filament cylinders, and the winding speed is 3500m/min, so that the dyeing-easy oxidation resistant nylon filament is prepared.
Comparative example 5
In contrast to example 3, steps S3, S4 were not performed, and the conjugate was replaced with a modified porous silica nanosphere in step S5.
The method comprises the following steps:
S1, dissolving 13g of ethyl orthosilicate in 200mL of dichloromethane to obtain a solution A, dissolving 1.5g of an oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and 0.8g of Tween-85 in 300mL of water to obtain a solution B, dropwise adding the solution A into the solution B, emulsifying for 15min at 7000r/min, adjusting the pH value of the solution to 9.5, stirring and reacting for 11h, centrifuging, washing and drying to obtain the porous silica nanospheres;
s2, adding 11g of porous silica nanospheres into 200mL of water, adding 5g of dopamine hydrochloride and 1.5g of catalyst, heating to 50 ℃, stirring and reacting for 4 hours, centrifuging, washing and drying to obtain modified porous silica nanospheres;
the catalyst is Tris-HCl solution with pH=9;
s3, adding 10g of modified porous silica nanospheres into 40mL of graphene oxide aqueous dispersion, performing 1000W ultrasonic dispersion for 10min, and performing spray drying to obtain a fold type coating modifier;
S4, heating 100g of caprolactam to 75 ℃ for melting, adding 1.5g of aminocaproic acid and 10g of fold type coating modifier, stirring and mixing for 15min, heating, decompressing and stirring for reaction at 250 ℃ at the speed of 120r/min under the pressure of 0.05MPa for 4h, discharging, cooling, drying and slicing to obtain nylon slices;
S5, conveying nylon chips into a screw extruder, heating to 290 ℃ to obtain a melt, pressurizing and conveying the melt to a spinning box, metering the melt by a metering pump, spraying the melt through a spinning component, wherein the fineness of the sprayed filaments is 0.1mm, cooling the filaments by side blowing to form filament bundles, eliminating static electricity by oiling the cooled filament bundles, controlling the attached quantity of the oil to be 1%, carrying out drafting shaping treatment on the oiled filament bundles, and carrying out 2-stage stretching and 2-stage shaping on the drafting shaping filament bundles, wherein the temperature of the 1 st pair of hot rolls is 35 ℃, the temperature of the 2 nd pair of hot rolls is 50 ℃, the 1 st pair of hot rolls and the 2 nd pair of hot rolls are used for preheating the filament bundles, the stretching ratio is 1 time, and winding the shaped filament bundles into filament cylinders, and the winding speed is 3500m/min, so that the dyeing-easy oxidation resistant nylon filament is prepared.
Test example 1 yellow index test
The easy-to-dye antioxidant nylon filaments prepared in examples 1-3 or comparative examples 1-5 were placed in a ventilated heat aging laboratory box, the temperature of the aging box was set to 180 ℃, the opening of the ventilation valve was 1/2, and ventilation was performed by air blowing. Taking out the sample to be tested after 120min interval, and measuring the yellow index (YI value) by CM-3600d spectrocolorimetry according to HG/3862-2006.
The results are shown in Table 1.
TABLE 1
| Group of | Yellow index (YI value) |
| Example 1 | 12.1 |
| Example 2 | 11.9 |
| Example 3 | 11.4 |
| Comparative example 1 | 12.4 |
| Comparative example 2 | 27.5 |
| Comparative example 3 | 23.9 |
| Comparative example 4 | 14.5 |
| Comparative example 5 | 34.8 |
As shown in the table above, the easy-to-dye antioxidant nylon filaments prepared in examples 1-3 of the invention have very low yellow values and have good color change resistance.
Test example 2
The easy-to-dye antioxidant nylon filaments prepared in examples 1-3 or comparative examples 1-5 were placed in a ventilated heat aging laboratory box, the temperature of the aging box was set to 180 ℃, the opening of the ventilation valve was 1/2, and ventilation was performed by air blowing. And taking out the sample to be tested after 120min interval, and testing the breaking strength and breaking elongation of the sample to be tested before and after the thermal oxidation aging test.
The results are shown in Table 2.
TABLE 2
As can be seen from the above table, the easy-dyeing oxidation-resistant nylon filaments prepared in examples 1 to 3 of the present invention have good mechanical properties and oxidation resistance.
Test example 3
The easy-to-dye antioxidant nylon filaments prepared in examples 1-3 or comparative examples 1-5 were subjected to performance testing.
The results are shown in Table 3.
TABLE 3 Table 3
| Group of | Heat shrinkage (%) | Coefficient of linear density variation (%) |
| Example 1 | 1.7 | 0.44 |
| Example 2 | 1.8 | 0.45 |
| Example 3 | 1.5 | 0.42 |
| Comparative example 1 | 2.0 | 0.48 |
| Comparative example 2 | 2.7 | 0.54 |
| Comparative example 3 | 3.3 | 0.87 |
| Comparative example 4 | 5.9 | 1.95 |
| Comparative example 5 | 7.8 | 2.89 |
As shown in the table above, the easy-dyeing antioxidant nylon filaments prepared in examples 1-3 of the invention have good comprehensive properties.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
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