Anti-aging polyvinyl dyed fiber and preparation method thereof

Abstract

The invention discloses an anti-aging polyvinyl dyed fiber and a preparation method thereof, belongs to the technical field of polyvinyl fiber processing, and is used for solving the technical problem that the mechanical strength and the anti-aging performance of the polyvinyl dyed fiber in the prior art need to be further improved. The invention relates to a PE-g-MAH (polyethylene-graft-maleic anhydride) anti-aging material, which specifically comprises the following components in parts by weight: 60-70 parts of a polyethylene copolymer, 10-15 parts of PE-g-MAH, 8-12 parts of an anti-aging filler, 1-2 parts of an azo coloring agent and 3-4 parts of an additive. The polyvinyl dyed fiber is prepared by constructing a copolymerization matrix containing functional group modified polyethylene, hyperbranched epoxy modified zinc oxide and a hindered amine composite anti-aging system and taking PE-g-MAH as a compatilizer, so that the mechanical strength of the polyvinyl dyed fiber is effectively improved, and the polyvinyl dyed fiber has excellent anti-aging performance under an ultraviolet aging condition. The excellent mechanical property and extremely low color difference can be kept, and good aging resistance is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyvinyl fiber processing, and particularly relates to an aging-resistant polyvinyl dyeing fiber and a preparation method thereof. BACKGROUND

[0002] Polyethylene fibers have the characteristics of low density, good chemical stability, excellent wet heat resistance, etc., and are widely used in geotextiles, outdoor decorative materials, protective fabrics and industrial fibers, etc. fields. The traditional polyethylene molecular chain has high regularity, low polarity and small surface energy. In the long-term light environment, the main chain is prone to breakage, crosslinking and pulverization, which leads to rapid decay of mechanical properties. The anti-ultraviolet aging performance of polyethylene fiber is poor. The non-polarity of polyethylene makes it weak in adsorption of organic dyes, and the dyeing agent is difficult to be effectively fixed in the fiber matrix, resulting in poor dyeing uniformity and insufficient color fastness, especially obvious fading in outdoor weather environment.

[0003] At present, the aging resistance of polyethylene fibers can be improved by adding light stabilizers, introducing inorganic fillers or using blended modified polymers. However, the inorganic aging-resistant fillers do not match the polarity of the polyethylene matrix, and the fillers are prone to agglomeration and uneven dispersion, which further affects the mechanical properties and weather resistance of the fibers. And single ultraviolet absorber or hindered amine light stabilizer usually has the problems of easy migration and poor durability, which is difficult to maintain stable effect in long-term ultraviolet irradiation environment. In terms of dyeing, due to the lack of polar groups in polyethylene, the compatibility of polyethylene with azo or disperse dyes is poor, which leads to the migration or decomposition of dyes under the action of light and heat, and cannot meet the requirements of high fastness dyeing fibers. SUMMARY

[0004] The present application aims to provide an aging-resistant polyvinyl dyeing fiber and a preparation method thereof, which solves the technical problem that the mechanical strength and aging resistance of the polyvinyl dyeing fiber in the prior art need to be further improved.

[0005] The purpose of the present application can be achieved by the following technical scheme: an aging-resistant polyvinyl dyeing fiber, comprising the following components by weight: 60-70 parts of polyethylene copolymer, 10-15 parts of PE-g-MAH, 8-12 parts of aging-resistant filler, 1-2 parts of azo dyeing agent and 3-4 parts of additive.

[0006] The preparation method of the polyethylene copolymer is as follows: low-density polyethylene, styrene, perfluorobutyl vinyl, 4-vinyl aniline and initiator are added to a twin-screw extruder, melt mixed for 2-3 min, then extruded, cooled and solidified, crushed, and then passed through a 20-mesh screen to obtain the polyethylene copolymer.

[0007] Further, the weight ratio of the low-density polyethylene, styrene, perfluorobutyl ethylene, 4-vinyl aniline, and initiator is 100:1.8-2:0.9-1.1:2.8-3.2:0.5-0.6, the initiator is benzoyl peroxide, and the temperature of the six temperature zones of the twin-screw extruder is 135℃, 140℃, 140℃, 145℃, 145℃, and 145℃ in sequence, and the main shaft rotation speed of the twin-screw extruder is 10-15r / min.

[0008] Further, the azo dye is composed of one or more of azo pigment red, azo pigment yellow, and azo pigment blue; and the additive agent is composed of dispersant, lubricant, plasticizer, antioxidant, and antistatic agent in a weight ratio of 3:1:4:2:1, the dispersant is stearate, the lubricant is ethylene bis-stearamide, the plasticizer is phthalate, the antioxidant is antioxidant 1010, and the antistatic agent is antistatic agent SN.

[0009] Further, the preparation method of the anti-aging filler is as follows: mixing hyperbranched epoxy modified zinc oxide, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, and N,N-dimethylformamide, heating the reaction system to 70-80℃, and keeping the reaction for 60-80min, and then treating to obtain the anti-aging filler.

[0010] The synthesis reaction mechanism of the anti-aging filler is as follows:

[0011]

[0012] Further, the dosage ratio of the hyperbranched epoxy modified zinc oxide, 4-aminomethyl-2,2,6,6-tetramethylpiperidine, and N,N-dimethylformamide is 5g:3-4g:30mL, the post-treatment includes: after the reaction is completed, cooling the reaction system to room temperature, filtering, washing the filter cake with acetone for 3 times, then drying, transferring the filter cake to a drying box with a temperature of 60-70℃, and drying to constant weight to obtain the anti-aging filler.

[0013] Further, the hyperbranched epoxy modified zinc oxide is obtained by the following steps:

[0014] A1, under the protection of inert gas atmosphere, mixing and stirring propyl triethoxysilane isocyanate and tetrahydrofuran, heating the reaction system to 40-50℃, adding 6-amino-2-hydroxymethyl-n-hexane-1-alcohol into the reaction system, keeping the reaction for 50-60min, adding lye into the reaction system, then adding nano zinc oxide into the reaction system, keeping the reaction for 60-80min, and then treating to obtain activated zinc oxide;

[0015] The synthesis reaction formula of the activated zinc oxide is as follows:

[0016]

[0017] In the formula: The nano zinc oxide particles.

[0018] A2, the activated zinc oxide, epichlorohydrin and potassium hydroxide are mixed and stirred, the reaction system is heated to 70-80 DEG C, and is kept for 6-8 h, and then is treated to obtain the hyperbranched epoxy modified zinc oxide.

[0019] The synthesis reaction formula of the hyperbranched epoxy modified zinc oxide is:

[0020]

[0021] Further, in step A1, the 1g of the isocyanate propyl triethoxysilane, 10mL of the tetrahydrofuran, 2mL of the lye and 2.8-3.2g of the nano zinc oxide, the molar ratio of the 6-amino-2-hydroxymethyl n-hexane-1-alcohol and the isocyanate propyl triethoxysilane is 1:1, the lye is composed of 50mL of 3-5mol / L sodium hydroxide aqueous solution and 2g of sodium dodecyl sulfate, and the post-treatment comprises: after the reaction is completed, the reaction system is cooled to room temperature, is filtered, the filter cake is washed to neutral with purified water, and then is dried, the filter cake is transferred to a drying box with a temperature of 70-80 DEG C, and is dried to constant weight to obtain the activated zinc oxide.

[0022] Further, in step A2, the amount ratio of the activated zinc oxide, epichlorohydrin and potassium hydroxide is 1g:5mL:0.5g, and the post-treatment comprises: after the reaction is completed, the reaction system is cooled to room temperature, is filtered, the filter cake is washed with purified water for 3 times, and then is dried, the filter cake is transferred to a drying box with a temperature of 65-75 DEG C, and is dried to constant weight to obtain the hyperbranched epoxy modified zinc oxide.

[0023] In the present application, a preparation method of the polyethylene-based dyeing fiber is also provided, which comprises the following steps:

[0024] S1, the polyethylene copolymer, PE-g-MAH, anti-aging filler, azo dyeing agent and additive are premixed, and then are added into a double screw extruder, are melt-mixed for 2-3min to obtain a spinning melt;

[0025] S2, the spinning melt is conveyed to a melt spinning machine in a melt state, and is melt-spun to obtain a polyethylene-based dyeing fiber blank;

[0026] S3, the polyethylene-based dyeing fiber blank is subjected to 2-3 times of hot stretching, and then is set to obtain the polyethylene-based dyeing fiber.

[0027] Further, in step S1, the temperatures of the four temperature sections of the double screw extruder are 145 DEG C, 150 DEG C, 150 DEG C and 155 DEG C in sequence, and the rotation speed of the main shaft of the double screw extruder is 10-15 r / min; in step S2, the temperature of the melt spinning machine is 170-180 DEG C, the melt spinning is air-cooled solidification, the air-cooled air supply temperature is 20-25 DEG C, and the air blowing speed is 0.6-0.8 m / s; in step S3, the drawing temperature is 120-130 DEG C, the heat setting temperature is 130-140 DEG C, and the heat setting time is 30-60 s.

[0028] The present application has the following advantages:

[0029] 1. The present application introduces styrene, perfluorobutyl vinyl and 4-vinyl aniline and other comonomers into polyethylene, so that the polyethylene matrix has a comprehensive structure of aromatic rigid chain segment, fluorine-containing hydrophobic chain segment and polar active group, and the mechanical strength, light energy absorption capacity and oxidation stability of the matrix are enhanced; PE-g-MAH as a compatibilizer can react with the amine group of the copolymer and the epoxy end group of the anti-aging filler to form a stable interfacial bonding layer, so that the heterogeneous system realizes uniform dispersion and effective load transfer; the melt spinning, heat stretching and heat setting process makes the fiber obtain stable chain segment orientation and fine crystal structure, and exhibits high breaking strength and good ductility when not aging, which lays a structural foundation for subsequent anti-aging performance.

[0030] 2. The present application also constructs a three-dimensional hyperbranched structure on the surface of zinc oxide through silane activation and epoxy ring-opening reaction, so that the nano zinc oxide particles have high functionality and excellent dispersibility; the hyperbranched structure not only inhibits particle agglomeration through steric hindrance, but also forms chemical bonding with the polar groups of the matrix through multiple epoxy groups, thereby enhancing the stress transfer capacity of the inorganic-organic interface; in addition, the hindered amine light stabilizer is fixed on the hyperbranched layer to form a composite anti-aging system integrating inorganic light shielding-hyperbranched adhesive layer-HALS radical capture, so that the ultraviolet shielding and radical scavenging functions continuously and efficiently cooperate on the micro interface, thereby avoiding the migration and volatilization problems of traditional hindered amines, and significantly improving the durability of the stabilizer.

[0031] 3、The present application is to select azo pigment as colorant, by combining azo dyeing agent with the polar group of polyethylene copolymer, and using functional filler to optimize the adsorption and dispersion performance of the dye, improve the dyeing uniformity and color fastness; the light shielding effect of hyperbranched modified zinc oxide greatly reduces the effective light energy received by the pigment and the matrix; at the same time, the hindered amine light stabilizer fixed on the surface of the hyperbranched layer can capture free radicals generated by the absorption of a small amount of light energy in time, inhibit the rupture of azo structure and matrix yellowing, avoid the color shift of dyeing system due to photooxidation; the high stability of hyperbranched structure and the characteristics of interface immobilization make the light stabilizer no longer migrate, precipitate or decay with time, so as to ensure that the fiber maintains stable color coordinates under long-term ultraviolet irradiation, and improves the aging resistance of fiber material. DETAILED DESCRIPTION

[0032] The technical solutions of the present application will be described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0033] In the present application, the brand of low-density polyethylene is Daqing Petrochemical, the grade is 8320, and the processing level is blow molding grade and blow film grade;

[0034] In the present application, the nano zinc oxide is selected from the commercially available product of Qinghe County Chaotai Metal Material Co., Ltd., the particle size is 200 mesh, and the zinc oxide is ≥99.9%;

[0035] In the present application, PE-g-MAH is anhydride modified polyethylene, the brand is American DuPont, and the model is E528.

[0036] Example 1

[0037] The present application provides a preparation method of an aging-resistant polyethylene-based dyed fiber, which specifically comprises the following steps:

[0038] Step 1, preparation of polyethylene copolymer

[0039] Take: low-density polyethylene 5 kg, styrene 90 g, perfluorobutyl vinyl 45 g, 4-vinyl aniline 140 g, and initiator benzoyl peroxide 25 g, and add them into a double-screw extruder. The temperature of the six temperature sections of the double-screw extruder is set to 135℃, 140℃, 140℃, 145℃, 145℃, and 145℃ in turn. The main shaft rotation speed of the double-screw extruder is 10 r / min. After melting and mixing for 2 min, extrusion is carried out. After cooling and solidification, crushing is carried out, and then the product is passed through a 20-mesh screen to obtain the polyethylene copolymer.

[0040] In the reaction, by the action of free radical initiator and high temperature, styrene units, perfluorobutyl vinyl units and 4-vinyl aniline units are introduced on the low density polyethylene main chain. Styrene contains rigid aromatic ring, which improves the local rigidity of the molecular chain after being grafted to the polyethylene main chain, increases the mechanical strength and heat resistance of the polymer, and the aromatic ring itself has a certain absorption to ultraviolet light, which can partially dissipate the ultraviolet energy in the light environment, slow down the photodegradation process of the polyethylene main chain; the rigid side group moderately destroys the excessive crystallization of polyethylene, so that the material still maintains appropriate elongation rate while ensuring strength, which is beneficial to the balance of subsequent hot stretching orientation and fiber flexibility; perfluorobutyl vinyl contains high energy C-F bond and hydrophobic fluorine-containing segment, which significantly improves the stability of polymer segment to heat, oxygen and ultraviolet light after copolymerization, effectively inhibits chemical degradation under high energy irradiation; 4-vinyl aniline has both aromatic ring structure and polar amino group, the amino group is a strong polar group, which significantly improves the overall polarity of the polyethylene copolymer, so that the originally non-polar polyethylene matrix has higher affinity and adsorption capacity for organic dyestuff such as azo pigment red, promotes the more stable positioning of the dye inside the fiber, reduces the migration and volatility, and the existence of amino group and aromatic ring provides potential chemical binding or strong interaction sites for subsequent modification of epoxy group on the surface of hyperbranched epoxy modified zinc oxide and anhydride group in PE-g-MAH, enhances the interfacial bonding capacity between the matrix and the anti-aging filler and between the matrix and the compatibilizer, makes the filler more uniformly dispersed, and the interfacial strength is higher, thereby improving the overall mechanical stability and anti-aging ability of the fiber; the aromatic amine structure itself has a certain absorption and buffering effect on light, to a certain extent, it participates in the light stabilization mechanism, which helps to slow down the degradation of dye and polymer chain under light, and further reduces the color decay and mechanical property degradation.

[0041] Step 2, preparation of hyperbranched epoxy modified zinc oxide

[0042] Mix 3 mol / L sodium hydroxide aqueous solution and sodium dodecyl sulfate according to 50 mL:2 g to obtain lye;

[0043] Weigh: propyl triethoxysilane isocyanate 24.7 g and tetrahydrofuran 247 mL into an argon-protected reaction bottle and stir, heat the reaction bottle to 40 DEG C, add 6-amino-2-hydroxymethyl n-hexane-1-ol 14.7 g to the reaction bottle, and keep warm for 50 min, add lye 49.4 mL to the reaction bottle, stir for 2 min, add nano zinc oxide 69 g to the reaction bottle, keep warm for 60 min, cool the reaction bottle to room temperature, filter, wash the filter cake with purified water until it is neutral, then dry, transfer the filter cake to a drying box with a temperature of 70 DEG C, and dry to constant weight to obtain activated zinc oxide;

[0044] Take: activated zinc oxide 60 g, epichlorohydrin 300 mL and potassium hydroxide 30 g into the reaction bottle stirring, the reaction bottle heating to 70 ℃, keep the reaction for 6 h, the reaction bottle cooling to room temperature, filter, filter cake with pure water washing 3 times after dry, filter cake into the temperature of 65 ℃ drying box dry to constant weight, get hyperbranched epoxy modified zinc oxide.

[0045] In the reaction, propyl triethoxysilane isocyanate and 6-amino-2-hydroxymethyl n-hexanol undergo typical isocyanate-amino addition reaction to form a urea-containing organic silicon precursor, then the triethoxysilane groups on the molecule are hydrolyzed and condensed under the action of lye to form a polysiloxane coating outside the nano zinc oxide, and 6-amino-2-hydroxymethyl n-hexanol provides a flexible long chain and an additional hydroxyl group to form a surface organic layer with a multi-polar, multi-reaction site structure; under the catalysis of potassium hydroxide, epichlorohydrin and the hydroxyl groups on the surface modified alkyl chain segments of the activated zinc oxide undergo ring-opening reaction, and the chloropropanol groups after ring-opening further undergo dehydrochlorination reaction under alkaline conditions to form new epoxy end groups, thereby preparing the hyperbranched epoxy modified zinc oxide.

[0046] The zinc oxide core itself has strong ultraviolet absorption and scattering ability, and the high dispersibility brought by the hyperbranched layer makes the ultraviolet shielding effect spread throughout the material interior, improving the uniformity of ultraviolet protection; the hyperbranched organic surface avoids ZnO agglomeration, making the light shielding effect stable and not producing stress concentration; the epoxy groups in the hyperbranched epoxy structure react with the maleic anhydride in PE-g-MAH to form ester bonds or ether bonds; the polar groups such as amino and hydroxyl groups and the 4-vinyl aniline part in the copolymer undergo hydrogen bonding or dipole interaction, thereby forming a stable interface layer, so that the filler does not fall off, does not migrate, and the anti-aging effect is long-term stable; the hyperbranched epoxy layer has high specific surface area and rich polar groups, which can adsorb and disperse azo dyeing agents, reduce dye migration and enrichment, and thereby inhibit the photolysis of dyes caused by light.

[0047] Step 3, preparation of anti-aging filler

[0048] Take: hyperbranched epoxy modified zinc oxide 50 g, 4-aminomethyl-2,2,6,6-tetramethylpiperidine 30 g, N,N-dimethylformamide 300 mL into the reaction bottle stirring, the reaction bottle heating to 70 ℃, keep the reaction for 60 min, the reaction bottle cooling to room temperature, filter, filter cake with acetone washing 3 times after dry, filter cake into the temperature of 60 ℃ drying box dry to constant weight, get anti-aging filler.

[0049] In the reaction, the epoxy end groups contained on the surface of the hyperbranched epoxy modified zinc oxide undergo ring-opening reaction with the primary amino groups in the 4-aminomethyl-2,2,6,6-tetramethylpiperidine molecules to form β-hydroxylamine structure, forming a hindered amine modification, thereby preparing the anti-aging filler.

[0050] In the anti-aging filler, zinc oxide efficiently scatters and absorbs light energy in the UVA region, blocking the direct contact of light energy with the polyethylene segment; the hindered amine can capture free radicals in the photooxidation process, blocking the chain degradation reaction, and through the "no-organic" dual-effect synergistic mechanism, excellent anti-aging effect is achieved. The hyperbranched layer makes the ZnO particles highly dispersed, making the light shielding more uniform, and the multi-point combination makes the hindered amine not migrate and not volatile, playing a stable and long-lasting light stabilizing role.

[0051] Step 4, preparation of polyethylene-based dyed fibers

[0052] azo pigment red is used as the azo dyeing agent;

[0053] Zinc stearate, ethylene bis-stearamide, dibutyl phthalate, antioxidant 1010, and antistatic agent SN are mixed in a weight ratio of 3:1:4:2:1 to obtain an additive aid;

[0054] The polyethylene copolymer 60 parts, PE-g-MAH 10 parts, anti-aging filler 8 parts, azo dyeing agent 1 part, and additive aid 3 parts are weighed by weight parts and mixed into a twin-screw extruder. The temperature of the four temperature sections of the twin-screw extruder is set to 145℃, 150℃, 150℃, and 155℃, respectively. The main shaft rotation speed of the twin-screw extruder is 10r / min. The melt mixing is carried out for 2min to obtain a spinning melt. The spinning melt is transported to a melt spinning machine. The melt spinning temperature is set to 170℃. The melt spinning is carried out. The air cooling solidification is carried out. The air cooling blowing temperature is set to 20℃. The blowing rate is 0.6m / s. The polyethylene-based dyed fiber blank is obtained.

[0055] The polyethylene-based dyed fiber blank is placed in a 120℃ environment for 2 times heat stretching. Then it is placed in a heat setting machine with a temperature of 130℃. The heat setting time is set to 30s. The heat setting is carried out. The polyethylene-based dyed fiber with a diameter of 16-20μm is obtained.

[0056] Example 2

[0057] The present embodiment provides a preparation method of an anti-aging polyethylene-based dyed fiber, which specifically comprises the following steps:

[0058] Step 1, preparation of polyethylene copolymer

[0059] Low-density polyethylene 5kg, styrene 95g, perfluorobutyl vinyl 50g, 4-vinyl aniline 150g, and initiator benzoyl peroxide 27g are weighed and added into a twin-screw extruder. The temperature of the six temperature sections of the twin-screw extruder is set to 135℃, 140℃, 140℃, 145℃, 145℃, and 145℃, respectively. The main shaft rotation speed of the twin-screw extruder is 13r / min. After melt mixing for 2.5min, it is extruded. After cooling and solidification, it is crushed and passed through a 20 mesh screen to obtain the polyethylene copolymer.

[0060] Step 2, preparation of hyperbranched epoxy modified zinc oxide

[0061] Mix 4 mol / L sodium hydroxide aqueous solution and sodium dodecyl sulfate uniformly at 50 mL:2 g to obtain lye;

[0062] Take: isocyanate propyl triethoxysilane 24.7 g and tetrahydrofuran 247 mL, stir in an argon-protected reaction bottle, heat the reaction bottle to 45 DEG C, add 6-amino-2-hydroxymethyl n-hexane-1-ol 14.7 g to the reaction bottle, and keep the reaction for 55 min, add lye 49.4 mL to the reaction bottle, stir for 2.5 min, add nano zinc oxide 74 g to the reaction bottle, keep the reaction for 70 min, cool the reaction bottle to room temperature, filter, wash the filter cake with purified water until it is neutral, then dry, transfer the filter cake to a drying box with a temperature of 75 DEG C, and dry to constant weight to obtain activated zinc oxide;

[0063] Take: activated zinc oxide 60 g, epoxy chloropropane 300 mL and potassium hydroxide 30 g, stir in a reaction bottle, heat the reaction bottle to 75 DEG C, keep the reaction for 7 h, cool the reaction bottle to room temperature, filter, wash the filter cake with purified water for 3 times, then dry, transfer the filter cake to a drying box with a temperature of 70 DEG C, and dry to constant weight to obtain hyperbranched epoxy modified zinc oxide.

[0064] Step 3, preparation of anti-aging filler

[0065] Take: hyperbranched epoxy modified zinc oxide 50 g, 4-aminomethyl-2,2,6,6-tetramethylpiperidine 35 g, N,N-dimethylformamide 300 mL, stir in a reaction bottle, heat the reaction bottle to 75 DEG C, keep the reaction for 70 min, cool the reaction bottle to room temperature, filter, wash the filter cake with acetone for 3 times, then dry, transfer the filter cake to a drying box with a temperature of 65 DEG C, and dry to constant weight to obtain anti-aging filler.

[0066] Step 4, preparation of polyvinyl dyed fiber

[0067] Use azo pigment yellow as azo dyeing agent;

[0068] Mix calcium stearate, ethylene bis-stearamide, diisobutyl phthalate, antioxidant 1010 and antistatic agent SN according to the weight ratio of 3:1:4:2:1 to obtain additive aid;

[0069] The polyethylene copolymer 65 parts, PE-g-MAH 13 parts, anti-aging filler 10 parts, azo dyeing agent 1.5 parts and additive aid 3.5 parts by weight are mixed and added into a twin-screw extruder, the temperature of four temperature sections of the twin-screw extruder is set to 145℃, 150℃, 150℃ and 155℃ in turn, the main shaft rotation speed of the twin-screw extruder is 13r / min, and the melt mixing is carried out for 2.5min to obtain a spinning melt; the spinning melt is transported into a melt spinning machine, the melt spinning temperature is set to 175℃, melt spinning is carried out, air cooling is used, the air cooling air supply temperature is set to 23℃, and the blowing speed is 0.7m / s to obtain polyethylene-based dyed fiber blanks;

[0070] The polyethylene-based dyed fiber blanks are placed in an environment of 125℃ for 2.5 times heat stretching, and then are placed in a heat setting machine with a temperature of 135℃, the heat setting time is set to 45s, heat setting is carried out, and polyethylene-based dyed fibers with a diameter of 16-20μm are obtained.

[0071] Example 3

[0072] The present embodiment provides a preparation method of an anti-aging polyethylene-based dyed fiber, which specifically comprises the following steps:

[0073] Step 1, preparation of polyethylene copolymer

[0074] The low-density polyethylene 5kg, styrene 100g, perfluorobutyl vinyl 55g, 4-vinyl aniline 160g and initiator benzoyl peroxide 30g are weighed and added into a twin-screw extruder, the temperature of six temperature sections of the twin-screw extruder is set to 135℃, 140℃, 140℃, 145℃, 145℃ and 145℃ in turn, the main shaft rotation speed of the twin-screw extruder is 15r / min, melt mixing is carried out for 3min, then extrusion is carried out, cooling and solidification are carried out, and then the product is crushed and passed through a 20-mesh screen to obtain the polyethylene copolymer.

[0075] Step 2, preparation of hyperbranched epoxy modified zinc oxide

[0076] The 5mol / L sodium hydroxide aqueous solution and sodium dodecyl sulfate are mixed uniformly at 50mL:2g to obtain a lye;

[0077] The isocyanate propyl triethoxysilane 24.7g and tetrahydrofuran 247mL are weighed and added into an argon-protected reaction bottle and stirred, the reaction bottle is heated to 50℃, 6-amino-2-hydroxymethyl n-hexane-1-ol 14.7g is added into the reaction bottle, and the reaction is carried out for 60min, the lye 49.4mL is added into the reaction bottle, stirred for 3min, the nano zinc oxide 79g is added into the reaction bottle, and the reaction is carried out for 80min, the reaction bottle is cooled to room temperature, and then filtration is carried out, the filter cake is washed with purified water until it is neutral, and then is dried, the filter cake is transferred into a drying oven with a temperature of 80℃, and dried to constant weight to obtain the activated zinc oxide.

[0078] Weighing: activated zinc oxide 60 g, epichlorohydrin 300 mL and potassium hydroxide 30 g are added to the reaction bottle and stirred, the reaction bottle is heated to 80℃, and the reaction is kept for 8 h, the reaction bottle is cooled to room temperature, filtered, the filter cake is washed with purified water for 3 times and then dried, the filter cake is transferred to a drying box with a temperature of 75℃ and dried to constant weight, to obtain hyperbranched epoxy modified zinc oxide.

[0079] Step 3, preparation of anti-aging filler

[0080] Weighing: hyperbranched epoxy modified zinc oxide 50 g, 4-aminomethyl-2,2,6,6-tetramethylpiperidine 40 g, N,N-dimethylformamide 300 mL are added to the reaction bottle and stirred, the reaction bottle is heated to 80℃, and the reaction is kept for 80 min, the reaction bottle is cooled to room temperature, filtered, the filter cake is washed with acetone for 3 times and then dried, the filter cake is transferred to a drying box with a temperature of 70℃ and dried to constant weight, to obtain anti-aging filler.

[0081] Step 4, preparation of polyethylene-based dyed fiber

[0082] azo pigment red, azo pigment yellow and azo pigment blue are used as azo dyeing agent;

[0083] Sodium stearate, ethylene bis-stearamide, diisopropyl phthalate, antioxidant 1010 and antistatic agent SN are mixed according to the weight ratio of 3:1:4:2:1 to obtain additive aid;

[0084] Weighing: polyethylene copolymer 70 parts, PE-g-MAH 15 parts, anti-aging filler 12 parts, azo dyeing agent 2 parts and additive aid 4 parts are mixed and added to the twin-screw extruder, the temperature of the four temperature sections of the twin-screw extruder is set to 145℃, 150℃, 150℃ and 155℃ respectively, the main shaft rotation speed of the twin-screw extruder is 15 r / min, and the melt mixing is carried out for 3 min to obtain spinning melt; the spinning melt is transported to the melt spinning machine, the melt spinning temperature is set to 180℃, melt spinning is carried out, air cooling is used for solidification, the air cooling air supply temperature is set to 25℃, and the blowing rate is 0.8 m / s to obtain polyethylene-based dyed fiber blank.

[0085] The polyethylene-based dyed fiber blank is placed in an environment of 130℃ for 3 times heat stretching, and then it is placed in a heat setting machine with a temperature of 140℃, the heat setting time is set to 60 s, and heat setting is carried out to obtain polyethylene-based dyed fiber with a diameter of 16-20 μm.

[0086] Comparative Example 1

[0087] The difference between this comparative example and Example 3 is that step 1 is cancelled, and the low-density polyethylene in step 1 is replaced by polyethylene copolymer in step 4.

[0088] Comparative Example 2

[0089] The difference between this comparative example and Example 3 is that in Step 2, 2-(aminomethyl)propane-1,3-diol is used instead of 6-amino-2-hydroxymethyl-n-hexan-1-ol in equimolar amount.

[0090] Comparative Example 3

[0091] The difference between this comparative example and Example 3 is that in Step 4, PE-g-MAH is not added.

[0092] Performance test:

[0093] The polyvinyl dyed fibers prepared in Examples 1-3 and Comparative Examples 1-3 are laid flat at a laying density of 100 g / m2, and then placed in an irradiation box at a temperature of 50-60℃, a UVA-340 lamp is selected, and irradiation is carried out at an irradiation dose of 162 w / m2 to obtain the fiber samples after accelerated aging; 2

[0094] The breaking strength and elongation at break of the fiber samples before and after accelerated aging are determined according to the standard GB / T 14344-2022 "Chemical fibers - Filament tensile property test method".

[0095] The CIELAB color difference of the fiber samples before and after accelerated aging is determined according to the standard GB / T 250-2008 "Textiles - Color fastness test - Evaluation of color change with gray scale", and the specific test data are shown in Table 1 below.

[0096] Table 1 - Performance test data table of the sample

[0097]

[0098] Data analysis:

[0099] Comparative analysis of the data in Table 1 above, the breaking strength of the polyvinyl dyed fibers prepared by the present application reaches 4.72-4.78 cN / dtex, and the elongation at break reaches 25.3-26.2%. After irradiation accelerated aging, the breaking strength of the sample reaches 4.01-4.08 cN / dtex, the elongation at break reaches 20.2-21.0%, and the CIELAB color difference decreases to 0.6. The performance test data are all better than those of the comparative examples, indicating that by constructing a copolymer matrix containing a functional group modified polyethylene, a hyperbranched epoxy modified zinc oxide and a hindered amine composite anti-aging system, and using PE-g-MAH as a compatibilizer, the polyvinyl dyed fibers prepared by the present application not only effectively improve the mechanical strength of the polyvinyl dyed fibers, but also enable them to maintain excellent mechanical properties and extremely low color difference under ultraviolet aging conditions, and have good anti-aging performance.

[0100] ​The preferred embodiments of the application disclosed above are only to facilitate the elucidation of the application. The preferred embodiments do not describe all the details of the application and limit the application to the specific embodiments. Obviously, many modifications and variations can be made in light of the teachings above. The description is chosen and described in order to provide the best illustration of the application and its practical application to those skilled in the art and to enable those skilled in the art to utilize the application in its best mode. The application is only limited by the claims and their full scope and equivalents.

Claims

1. An aged-resistant polyvinyl dyed fiber, characterized by, The composition comprises the following components by weight parts: polyethylene copolymer 60-70 parts, PE-g-MAH 10-15 parts, anti-aging filler 8-12 parts, azo dyeing agent 1-2 parts and additive 3-4 parts; The preparation method of the polyethylene copolymer is as follows: low-density polyethylene, styrene, perfluorobutyl vinyl, 4-vinyl aniline and initiator are added into a double-screw extruder, melt-mixed for 2-3 min, then extruded, cooled and solidified, crushed, and screened through a 20-mesh screen to obtain the polyethylene copolymer.

2. The weatherable polyethylene-based colored fiber of claim 1, wherein, The weight ratio of the low-density polyethylene, styrene, perfluorobutyl vinyl, 4-vinyl aniline and initiator is 100:1.8-2:0.9-1.1:2.8-3.2:0.5-0.6, the initiator is benzoyl peroxide, the temperature of the six temperature zones of the double-screw extruder is 135℃, 140℃, 140℃, 145℃, 145℃ and 145℃ in sequence, and the main shaft rotation speed of the double-screw extruder is 10-15 r / min.

3. The weatherable polyethylene-based colored fiber of claim 1, wherein, The azo dyeing agent is composed of one or more of azo pigment red, azo pigment yellow and azo pigment blue; the additive is composed of dispersant, lubricant, plasticizer, antioxidant and antistatic agent in a weight ratio of 3:1:4:2:1, the dispersant is stearate, the lubricant is ethylene bis-stearamide, the plasticizer is phthalate, the antioxidant is antioxidant 1010, and the antistatic agent is antistatic agent SN.

4. The weatherable polyethylene-based colored fiber of claim 1, wherein, The preparation method of the anti-aging filler is as follows: hyperbranched epoxy modified zinc oxide, 4-aminomethyl-2,2,6,6-tetramethylpiperidine and N,N-dimethylformamide are mixed, the reaction system is heated to 70-80℃, and then incubated for 60-80 min, and then post-treated to obtain the anti-aging filler.

5. The weatherable polyethylene-based colored fiber of claim 4, wherein, The dosage ratio of the hyperbranched epoxy modified zinc oxide, 4-aminomethyl-2,2,6,6-tetramethylpiperidine and N,N-dimethylformamide is 5g:3-4g:30mL.

6. The weatherable polyethylene-based colored fiber of claim 4, wherein, The hyperbranched epoxy modified zinc oxide is obtained by the following steps: A1, under the protection of inert gas atmosphere, propyl triethoxysilane isocyanate and tetrahydrofuran are mixed and stirred, the reaction system is heated to 40-50℃, 6-amino-2-hydroxymethyl-n-hexane-1-alcohol is added into the reaction system, and then incubated for 50-60 min, lye is added into the reaction system, then nano-zinc oxide is added into the reaction system, and then incubated for 60-80 min, and then post-treated to obtain activated zinc oxide; A2, the activated zinc oxide, epichlorohydrin and potassium hydroxide are mixed and stirred, the reaction system is heated to 70-80℃, and then incubated for 6-8 h, and then post-treated to obtain the hyperbranched epoxy modified zinc oxide.

7. The weatherable polyethylene-based colored fiber of claim 6, wherein, In step A1, the dosage of propyl triethoxysilane isocyanate, tetrahydrofuran, lye and nano-zinc oxide is 1g:10mL:2mL:2.8-3.2g, the molar ratio of 6-amino-2-hydroxymethyl-n-hexane-1-alcohol and propyl triethoxysilane isocyanate is 1:1, and the lye is composed of 3-5 mol / L sodium hydroxide aqueous solution and sodium dodecyl sulfate in a ratio of 50mL:2g.

8. The weatherable polyethylene-based colored fiber of claim 6, wherein, In step A2, the amount ratio of the activated zinc oxide, epichlorohydrin and potassium hydroxide is 1g:5mL:0.5g.

9. A process for the production of a weatherable polyvinyl dyed fibre as claimed in any one of claims 1 to 8 characterised in that, The method comprises the following steps: S1, polyethylene copolymer, PE-g-MAH, anti-aging filler, azo dyeing agent and additive are premixed and then added into a double screw extruder, melt mixed for 2-3min to obtain a spinning melt; S2, the spinning melt is transported to a melt spinning machine in a melt state to melt spin and obtain polyethylene base dyeing fibers; S3, the polyethylene base dyeing fibers are heat stretched by 2-3 times and then shaped to obtain polyethylene base dyeing fibers.

10. The process for the preparation of an age resistant polyvinyl dyed fibre as claimed in claim 9, wherein, In step S1, the temperature of four temperature sections of the double screw extruder is 145℃, 150℃, 150℃ and 155℃ in sequence, and the main shaft rotation speed of the double screw extruder is 10-15r / min; in step S2, the temperature of the melt spinning machine is 170-180℃, the melt spinning is air-cooled solidification, the air-cooled air supply temperature is 20-25℃, and the air blowing rate is 0.6-0.8m / s; in step S3, the stretching temperature is 120-130℃, the heat setting temperature is 130-140℃, and the heat setting time is 30-60s.

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