CN111748868A - Anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber and preparation method thereof - Google Patents
Anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an anti-ultraviolet enhanced PE/PET composite elastic short fiber and a preparation method thereof, wherein the anti-ultraviolet enhanced PE/PET composite elastic short fiber is prepared from the following raw materials in parts by weight: 30-50 parts of PE, 30-50 parts of PET, 8-15 parts of graphene, 10-18 parts of modified carbon nanofiber, 8-15 parts of a high elasticity agent, 6-10 parts of an anti-ultraviolet agent, 5-10 parts of a toughening agent, 3-8 parts of a compatilizer, 2-5 parts of an antioxidant and 0.1-2.5 parts of other additives. According to the invention, through selecting raw material compositions, optimizing the content of each raw material, and selecting PE, PET, graphene, modified carbon nanofiber, a high elasticity agent, an anti-ultraviolet agent, a toughening agent, a compatilizer, an antioxidant and an auxiliary agent in a proper proportion, the advantages of the PE, the PET, the modified carbon nanofiber, the high elasticity agent, the anti-ultraviolet agent, the toughening agent, the compatilizer, the antioxidant and the auxiliary agent are fully exerted, mutually supplemented and mutually promoted, so that the anti-ultraviolet enhanced PE/PET composite elastic short fiber prepared by the invention has the advantages of strong anti-ultraviolet property, high elasticity, high fiber.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to an anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber and a preparation method thereof.
Background
Polyethylene terephthalate (PET for short) was the earliest polyester material to be industrialized, but was almost used for synthetic fibers at the beginning; after the 80s, PET was gradually used as engineering plastic and as thermoplastic polyester together with polybutylene terephthalate (PBT) as one of five major engineering plastics after the nucleating agent and crystallization promoter were successively developed.
In recent years, the yield of PET fibers is in a continuous growth situation, and with the increase of industrial investment, technical breakthrough and scale accumulation, the PET fiber industry will be more developed in the foreseeable future. The quality requirements of people on the non-woven fabrics are gradually improved, the environmental protection performance and the functionality become two major aspects which are increasingly regarded by people, the traditional non-woven fabrics cannot meet the requirements of the modern market, and the research and development of the functional composite fibers become the main development direction of the modern fibers.
The PET fiber can be used at 70-170 ℃, is the best in synthetic fiber in heat resistance and heat stability, but has a small difference in elasticity compared with natural fiber, poor wrinkle resistance, easy wrinkle and poor shape retention. And along with the improvement of living standard of people, the requirements on the non-woven fabrics are higher and higher, and the PET fiber can not meet the requirements of people due to the defects. The PET composite fiber has the advantages of soft hand feeling and high strength, but is not high in quality, difficult to dye, high in defective rate and low in elasticity.
In addition, with the industrial development, the degree of environmental pollution increases, halogen-containing compounds such as freon are emitted, and the ultraviolet transmittance increases due to the rarefied atmosphere, so that the ultraviolet protection is inevitable, and ultraviolet resistant fibers are becoming popular. At present, people develop product development in the fields of ultraviolet resistance and flame retardance, but the development is only limited to unilaterally carry out ultraviolet resistance or elastic modification on fibers, and how to organically combine the ultraviolet resistance and the elastic modification cannot be solved, so that the multifunctional fiber with wide application range is obtained.
In summary, the functional composite fibers currently used in the market still have the following technical problems:
1. the composite fiber has poor ultraviolet resistance and low protection level;
2. the poor compatibility among the composite fibers leads to the reduction of the mechanical properties of the composite fibers;
3. the composite fiber has poor toughness, low breaking strength and low mechanical strength;
4. the elasticity of the composite fiber is low, and the wrinkle resistance is poor, so that the product is easy to wrinkle and has poor shape retention.
Disclosure of Invention
Based on the above situation, the present invention aims to provide an anti-ultraviolet enhanced PE/PET composite elastic short fiber and a preparation method thereof, which can effectively solve the above problems.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber is composed of the following raw materials in parts by weight: the composite material comprises, by weight, 30-50 parts of PE, 30-50 parts of PET, 8-15 parts of graphene, 10-18 parts of modified carbon nanofibers, 8-15 parts of a high elasticity agent, 6-10 parts of an anti-ultraviolet agent, 5-10 parts of a toughening agent, 3-8 parts of a compatilizer, 2-5 parts of an antioxidant and 0.1-2.5 parts of other additives.
Preferably, the intrinsic viscosity of the PE is 0.7-1.1 dl/g, and the intrinsic viscosity of the PET is 0.5-1.2 dl/g.
Preferably, the high elasticity agent is composed of the following raw materials in parts by weight: 40-50 parts of chlorinated polyethylene elastomer, 20-28 parts of polyurethane elastomer, 3-5 parts of glass fiber, 5-10 parts of ethylene propylene diene monomer, 1-2 parts of bismuth carboxylate and 5-7 parts of carbon fluoride.
Preferably, the uvioresistant agent is a compound of zinc oxide, titanium dioxide and aluminum oxide according to the mass ratio of 1:1:1.5, wherein the average particle size of the zinc oxide is 200-350 nm, the average particle size of the titanium dioxide is 300-400 nm, and the average particle size of the aluminum oxide is 250-500 nm.
Preferably, the compatilizer is one or more of PE-g-ST, EPDM-g-GMA, ABS-g-MAH, POE-g-MAH and PP-g-MAH.
Preferably, the toughening agent is one or more of a styrene-butadiene thermoplastic elastomer, a carboxyl-terminated liquid nitrile rubber, a methyl methacrylate-butadiene-styrene terpolymer and a maleic anhydride grafted polyolefin elastomer, wherein the grafting rate of maleic anhydride is 5-25%.
Preferably, the antioxidant is a compound of a hindered amine antioxidant, a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:2: 1.
Preferably, the auxiliary agent comprises a nucleating agent and a lubricant; the nucleating agent is one or more of talcum powder, nano silicon dioxide, nano montmorillonite, sodium bicarbonate and sodium benzoate, and the lubricant is one or more of zinc stearate, calcium stearate, pentaerythritol stearate and silicone powder.
The invention also provides a preparation method of the anti-ultraviolet enhanced PE/PET composite elastic short fiber, which comprises the following steps:
(A) respectively weighing chlorinated polyethylene elastomer, polyurethane elastomer, glass fiber, ethylene propylene diene monomer, bismuth carboxylate and carbon fluoride according to parts by weight, uniformly mixing, heating and reacting in a reaction furnace at the temperature of 140-150 ℃ for 5-8 h, taking out, and cooling to obtain the high-elasticity agent;
(B) respectively weighing PE, PET, graphene, modified carbon nanofiber, a high elasticity agent, an anti-ultraviolet agent, a toughening agent, a compatilizer, an antioxidant and an auxiliary agent according to the parts by weight for later use;
(C) drying PE in a blast drier for 1-3 hours at the temperature of 110-120 ℃, and drying PET in the blast drier for 2-4 hours at the temperature of 115-130 ℃ for later use;
(D) weighing the dried PE and PET, adding the PE and PET into a high-speed mixer, adding the graphene, the modified carbon nanofibers, the high-elasticity agent, the anti-ultraviolet agent, the toughening agent, the compatilizer, the antioxidant and the auxiliary agent according to the weight ratio, mixing and stirring for 5-15 minutes to obtain a mixed material;
(E) adding the blend into a double-screw extruder, and carrying out spinning, washing, oiling, curling, drying and cutting post-treatment processes to obtain composite short fibers; wherein the temperature of the screw extruder is 150-290 ℃, the aperture of a spinneret plate is 10-60 mu m, the length of a hole capillary is 400-600 mu m, the stretching ratio of a spray head is 2.6-3.0, the oiling rate of fibers is 0.3-0.4%, the length of an air gap is 50-200 mm, and the spinning speed is 150-180 m/min.
Preferably, the preparation method of the modified carbon nanofiber comprises the following steps:
(a) putting the carbon nanofibers into a low-temperature plasma instrument for processing for 25-100 s, wherein the processing power is 120-280W;
(b) soaking the treated carbon nanofibers in a beaker filled with mixed acid, wherein the mixed acid is composed of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of (3-5) to 1, then placing the beaker on a magnetic stirrer, reacting at normal temperature for 6-10 h, washing with deionized water until washing liquor is neutral, and then drying in vacuum at 100-120 ℃ for 24h to obtain acid oxidized carbon nanofibers;
(c) uniformly mixing ethanol and deionized water in a mass ratio of (5-8): 1 to obtain an ethanol aqueous solution, adding a silane coupling agent, fully stirring and uniformly mixing to obtain a silane coupling agent hydrolysate, dispersing the acid oxidized carbon nanofibers in the silane coupling agent hydrolysate, stirring or ultrasonically filtering out fibers, and drying to obtain the modified carbon nanofibers with the silane coupling agent coating.
Compared with the prior art, the invention also has the following advantages and beneficial effects:
according to the invention, through selecting raw materials, optimizing the content of each raw material and selecting PE, PET, graphene, modified carbon nanofiber, a high elasticity agent, an anti-ultraviolet agent, a toughening agent, a compatilizer, an antioxidant and an auxiliary agent in a proper proportion, the advantages of each raw material are fully exerted, and the raw materials complement each other and promote each other, so that the composite fiber prepared by the method has the advantages of strong antibacterial property, strong anti-ultraviolet property, high elasticity, excellent mechanical property and the like.
The graphene with a proper proportion is added into the composite fiber, and is matched with other components, so that a good synergistic effect is achieved, the excellent characteristics of the composite short fiber and the graphene can be sufficiently softened, the composite fiber has excellent physical properties such as hygroscopicity, dyeability, comfortableness and high strength, and the flexibility, the conductivity and the antibacterial property of the graphene are increased.
The composite fiber is added with the modified carbon nanofibers in a proper proportion, and the modified carbon nanofibers are matched with other components to play a good synergistic effect, so that the modified carbon nanofibers can be more uniformly dispersed in the whole system and are chemically bonded with the composite short fibers, the modified carbon nanofibers can be more firmly combined with the composite fiber, and the mechanical property of the composite fiber is improved. Compared with the uncoated modified carbon nanofiber, the strength of the single-filament breaking strength of the composite fiber is obviously improved, the flexibility of the uncoated modified carbon nanofiber is maintained, and the problems of interface wettability and compatibility between the modified carbon nanofiber and a composite fiber material matrix are solved.
The composite fiber is added with the high elastic agent in a proper proportion, the raw material composition of the composite fiber is optimized, the composite fiber is matched with other components, a good synergistic effect is achieved, the elasticity of the composite fiber is effectively improved, and the composite fiber is soft and comfortable in hand feeling.
The anti-ultraviolet agent with a proper proportion is added into the composite fiber, and the anti-ultraviolet agent is matched with other components to play a good synergistic effect, so that the composite fiber prepared by the invention has excellent aging resistance, and still has a good anti-ultraviolet function after being washed for many times.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
Example 1:
an anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber is composed of the following raw materials in parts by weight: the composite material comprises, by weight, 30-50 parts of PE, 30-50 parts of PET, 8-15 parts of graphene, 10-18 parts of modified carbon nanofibers, 8-15 parts of a high elasticity agent, 6-10 parts of an anti-ultraviolet agent, 5-10 parts of a toughening agent, 3-8 parts of a compatilizer, 2-5 parts of an antioxidant and 0.1-2.5 parts of other additives.
In the embodiment, the intrinsic viscosity of the PE is 0.7-1.1 dl/g, and the intrinsic viscosity of the PET is 0.5-1.2 dl/g.
In this embodiment, the high elasticity agent is composed of the following raw materials in parts by weight: 40-50 parts of chlorinated polyethylene elastomer, 20-28 parts of polyurethane elastomer, 3-5 parts of glass fiber, 5-10 parts of ethylene propylene diene monomer, 1-2 parts of bismuth carboxylate and 5-7 parts of carbon fluoride.
In the embodiment, the uvioresistant agent is a compound of zinc oxide, titanium dioxide and aluminum oxide according to a mass ratio of 1:1:1.5, wherein the average particle size of the zinc oxide is 200-350 nm, the average particle size of the titanium dioxide is 300-400 nm, and the average particle size of the aluminum oxide is 250-500 nm.
In this example, the compatibilizer is one or more of PE-g-ST, EPDM-g-GMA, ABS-g-MAH, POE-g-MAH, and PP-g-MAH.
In this embodiment, the toughening agent is one or more of a styrene-butadiene thermoplastic elastomer, a carboxyl-terminated liquid nitrile rubber, a methyl methacrylate-butadiene-styrene terpolymer, and a maleic anhydride grafted polyolefin elastomer, wherein the grafting ratio of maleic anhydride is 5-25%.
In this embodiment, the antioxidant is a complex of a hindered amine antioxidant, a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:2: 1.
In this embodiment, the adjuvants include a nucleating agent and a lubricant; the nucleating agent is one or more of talcum powder, nano silicon dioxide, nano montmorillonite, sodium bicarbonate and sodium benzoate, and the lubricant is one or more of zinc stearate, calcium stearate, pentaerythritol stearate and silicone powder.
A preparation method of anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber comprises the following steps:
(A) respectively weighing chlorinated polyethylene elastomer, polyurethane elastomer, glass fiber, ethylene propylene diene monomer, bismuth carboxylate and carbon fluoride according to parts by weight, uniformly mixing, heating and reacting in a reaction furnace at the temperature of 140-150 ℃ for 5-8 h, taking out, and cooling to obtain the high-elasticity agent;
(B) respectively weighing PE, PET, graphene, modified carbon nanofiber, a high elasticity agent, an anti-ultraviolet agent, a toughening agent, a compatilizer, an antioxidant and an auxiliary agent according to the parts by weight for later use;
(C) drying PE in a blast drier for 1-3 hours at the temperature of 110-120 ℃, and drying PET in the blast drier for 2-4 hours at the temperature of 115-130 ℃ for later use;
(D) weighing the dried PE and PET, adding the PE and PET into a high-speed mixer, adding the graphene, the modified carbon nanofibers, the high-elasticity agent, the anti-ultraviolet agent, the toughening agent, the compatilizer, the antioxidant and the auxiliary agent according to the weight ratio, mixing and stirring for 5-15 minutes to obtain a mixed material;
(E) adding the blend into a double-screw extruder, and carrying out spinning, washing, oiling, curling, drying and cutting post-treatment processes to obtain composite short fibers; wherein the temperature of the screw extruder is 150-290 ℃, the aperture of a spinneret plate is 10-60 mu m, the length of a hole capillary is 400-600 mu m, the stretching ratio of a spray head is 2.6-3.0, the oiling rate of fibers is 0.3-0.4%, the length of an air gap is 50-200 mm, and the spinning speed is 150-180 m/min.
In this embodiment, the preparation method of the modified carbon nanofibers comprises:
(a) putting the carbon nanofibers into a low-temperature plasma instrument for processing for 25-100 s, wherein the processing power is 120-280W;
(b) soaking the treated carbon nanofibers in a beaker filled with mixed acid, wherein the mixed acid is composed of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of (3-5) to 1, then placing the beaker on a magnetic stirrer, reacting at normal temperature for 6-10 h, washing with deionized water until washing liquor is neutral, and then drying in vacuum at 100-120 ℃ for 24h to obtain acid oxidized carbon nanofibers;
(c) uniformly mixing ethanol and deionized water in a mass ratio of (5-8): 1 to obtain an ethanol aqueous solution, adding a silane coupling agent, fully stirring and uniformly mixing to obtain a silane coupling agent hydrolysate, dispersing the acid oxidized carbon nanofibers in the silane coupling agent hydrolysate, stirring or ultrasonically filtering out fibers, and drying to obtain the modified carbon nanofibers with the silane coupling agent coating.
Example 2:
an anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber is composed of the following raw materials in parts by weight: the composite material comprises, by weight, 30 parts of PE, 35 parts of PET, 10 parts of graphene, 10 parts of modified carbon nanofibers, 8 parts of a high elasticity agent, 7 parts of an anti-ultraviolet agent, 8 parts of a toughening agent, 3 parts of a compatilizer, 3 parts of an antioxidant and 0.5 part of other additives.
In this example, the intrinsic viscosity of the PE was 0.7dl/g and the intrinsic viscosity of the PET was 0.5 dl/g.
In this embodiment, the high elasticity agent is composed of the following raw materials in parts by weight: 40 parts of chlorinated polyethylene elastomer, 20 parts of polyurethane elastomer, 5 parts of glass fiber, 5 parts of ethylene propylene diene monomer, 2 parts of bismuth carboxylate and 5 parts of carbon fluoride.
In this embodiment, the anti-ultraviolet agent is a compound of zinc oxide, titanium dioxide and aluminum oxide in a mass ratio of 1:1:1.5, wherein the average particle size of the zinc oxide is 200nm, the average particle size of the titanium dioxide is 300nm, and the average particle size of the aluminum oxide is 250 nm.
In this example, the compatibilizer was EPDM-g-GMA.
In this example, the toughening agent is a styrene-butadiene thermoplastic elastomer.
In this embodiment, the antioxidant is a complex of a hindered amine antioxidant, a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:2: 1.
In this embodiment, the adjuvants include a nucleating agent and a lubricant; the nucleating agent is talcum powder, and the lubricant is zinc stearate.
A preparation method of anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber comprises the following steps:
(A) respectively weighing chlorinated polyethylene elastomer, polyurethane elastomer, glass fiber, ethylene propylene diene monomer, bismuth carboxylate and carbon fluoride according to parts by weight, uniformly mixing, heating and reacting in a reaction furnace at the temperature of 140 ℃, keeping for 5 hours, taking out, and cooling to obtain the high-elasticity agent;
(B) respectively weighing PE, PET, graphene, modified carbon nanofiber, a high elasticity agent, an anti-ultraviolet agent, a toughening agent, a compatilizer, an antioxidant and an auxiliary agent according to the parts by weight for later use;
(C) drying PE at 110 deg.C for 1 hr in a forced air drier, and drying PET at 115 deg.C for 2 hr in a forced air drier;
(D) weighing the dried PE and PET, adding the PE and PET into a high-speed mixer, simultaneously adding the graphene, the modified carbon nanofibers, the high elasticity agent, the anti-ultraviolet agent, the toughening agent, the compatilizer, the antioxidant and the auxiliary agent according to the weight ratio, mixing and stirring for 8 minutes to obtain a mixed material;
(E) adding the blend into a double-screw extruder, and carrying out spinning, washing, oiling, curling, drying and cutting post-treatment processes to obtain composite short fibers; wherein the temperature of the screw extruder is 290 ℃, the aperture of a spinneret plate is 25 mu m, the length of a hole capillary is 400 mu m, the stretching ratio of a nozzle is 2.6, the oiling rate of the fiber is 0.3%, the length of an air gap is 100mm, and the spinning speed is 150 m/min.
In this embodiment, the preparation method of the modified carbon nanofibers comprises:
(a) putting the nano carbon fiber into a low-temperature plasma instrument for processing for 50s with the processing power of 200W;
(b) soaking the treated carbon nanofibers in a beaker filled with mixed acid, wherein the mixed acid is composed of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 3: 1, then placing the beaker on a magnetic stirrer, reacting for 6 hours at normal temperature, washing with deionized water until the washing solution is neutral, and then drying for 24 hours in vacuum at 100 ℃ to obtain acid oxidized carbon nanofibers;
(c) uniformly mixing ethanol and deionized water in a mass ratio of 5:1 to obtain an ethanol aqueous solution, adding a silane coupling agent, fully stirring and uniformly mixing to obtain a silane coupling agent hydrolysate, dispersing acid-oxidized carbon nanofibers in the silane coupling agent hydrolysate, stirring or ultrasonically treating, filtering out fibers, and drying to obtain the modified carbon nanofibers with the silane coupling agent coating.
Example 3:
an anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber is composed of the following raw materials in parts by weight: the composite material comprises, by weight, 40 parts of PE, 50 parts of PET, 15 parts of graphene, 10 parts of modified carbon nanofibers, 15 parts of a high elasticity agent, 10 parts of an anti-ultraviolet agent, 5 parts of a toughening agent, 3 parts of a compatilizer, 5 parts of an antioxidant and 1 part of other additives.
In this example, the intrinsic viscosity of the PE was 0.8dl/g and the intrinsic viscosity of the PET was 1 dl/g.
In this embodiment, the high elasticity agent is composed of the following raw materials in parts by weight: 45 parts of chlorinated polyethylene elastomer, 20 parts of polyurethane elastomer, 5 parts of glass fiber, 5 parts of ethylene propylene diene monomer, 1 part of bismuth carboxylate and 7 parts of carbon fluoride.
In this embodiment, the anti-ultraviolet agent is a compound of zinc oxide, titanium dioxide and aluminum oxide in a mass ratio of 1:1:1.5, wherein the average particle size of the zinc oxide is 300nm, the average particle size of the titanium dioxide is 350nm, and the average particle size of the aluminum oxide is 400 nm.
In this example, the compatibilizer was a mixture of POE-g-MAH and PP-g-MAH.
In this example, the toughening agent is a mixture of a styrene-butadiene thermoplastic elastomer and a carboxyl-terminated liquid nitrile rubber.
In this embodiment, the antioxidant is a complex of a hindered amine antioxidant, a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:2: 1.
In this embodiment, the adjuvants include a nucleating agent and a lubricant; the nucleating agent is a mixture of sodium bicarbonate and sodium benzoate, and the lubricant is a mixture of pentaerythritol stearate and silicone powder.
A preparation method of anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber comprises the following steps:
(A) respectively weighing chlorinated polyethylene elastomer, polyurethane elastomer, glass fiber, ethylene propylene diene monomer, bismuth carboxylate and carbon fluoride according to parts by weight, uniformly mixing, heating and reacting in a reaction furnace at the temperature of 150 ℃, keeping for 8 hours, taking out, and cooling to obtain the high-elasticity agent;
(B) respectively weighing PE, PET, graphene, modified carbon nanofiber, a high elasticity agent, an anti-ultraviolet agent, a toughening agent, a compatilizer, an antioxidant and an auxiliary agent according to the parts by weight for later use;
(C) drying PE at 120 deg.C for 3 hr in a forced air drier, and drying PET at 130 deg.C for 4 hr in a forced air drier;
(D) weighing the dried PE and PET, adding the PE and PET into a high-speed mixer, simultaneously adding the graphene, the modified carbon nanofibers, the high elasticity agent, the anti-ultraviolet agent, the toughening agent, the compatilizer, the antioxidant and the auxiliary agent according to the weight ratio, mixing and stirring for 15 minutes to obtain a mixed material;
(E) adding the blend into a double-screw extruder, and carrying out spinning, washing, oiling, curling, drying and cutting post-treatment processes to obtain composite short fibers; wherein the temperature of the screw extruder is 290 ℃, the aperture of a spinneret plate is 50 mu m, the length of a hole capillary is 600 mu m, the stretching ratio of a nozzle is 3.0, the oiling rate of the fiber is 0.4 percent, the length of an air gap is 180mm, and the spinning speed is 180 m/min.
In this embodiment, the preparation method of the modified carbon nanofibers comprises:
(a) putting the nano carbon fiber into a low-temperature plasma instrument for processing for 90s, wherein the processing power is 250W;
(b) soaking the treated carbon nanofibers in a beaker filled with mixed acid, wherein the mixed acid is composed of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 5:1, then placing the beaker on a magnetic stirrer, reacting for 10 hours at normal temperature, washing with deionized water until the washing solution is neutral, and then drying for 24 hours in vacuum at 120 ℃ to obtain acid oxidized carbon nanofibers;
(c) uniformly mixing ethanol and deionized water in a mass ratio of 8:1 to obtain an ethanol aqueous solution, adding a silane coupling agent, fully stirring and uniformly mixing to obtain a silane coupling agent hydrolysate, dispersing acid-oxidized carbon nanofibers in the silane coupling agent hydrolysate, stirring or ultrasonically treating, filtering out fibers, and drying to obtain the modified carbon nanofibers with the silane coupling agent coating.
Example 4:
an anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber is composed of the following raw materials in parts by weight: the composite material comprises, by weight, 2 parts of PE50 parts, 45 parts of PET, 12 parts of graphene, 15 parts of modified carbon nanofibers, 15 parts of a high elasticity agent, 10 parts of an anti-ultraviolet agent, 10 parts of a toughening agent, 8 parts of a compatilizer, 5 parts of an antioxidant and other additives.
In this example, the intrinsic viscosity of the PE was 1.1dl/g and the intrinsic viscosity of the PET was 0.8 dl/g.
In this embodiment, the high elasticity agent is composed of the following raw materials in parts by weight: 50 parts of chlorinated polyethylene elastomer, 25 parts of polyurethane elastomer, 5 parts of glass fiber, 5 parts of ethylene propylene diene monomer, 2 parts of bismuth carboxylate and 5 parts of carbon fluoride.
In this embodiment, the anti-ultraviolet agent is a compound of zinc oxide, titanium dioxide and aluminum oxide in a mass ratio of 1:1:1.5, wherein the average particle size of the zinc oxide is 350nm, the average particle size of the titanium dioxide is 350nm, and the average particle size of the aluminum oxide is 400 nm.
In this example, the compatibilizer was a mixture of PE-g-ST and EPDM-g-GMA.
In this example, the toughening agent was a mixture of a methylmethacrylate-butadiene-styrene terpolymer and a maleic anhydride grafted polyolefin elastomer, with a grafting of 20% maleic anhydride.
In this embodiment, the antioxidant is a complex of a hindered amine antioxidant, a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:2: 1.
In this embodiment, the adjuvants include a nucleating agent and a lubricant; the nucleating agent is sodium benzoate, and the lubricant is pentaerythritol stearate.
A preparation method of anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber comprises the following steps:
(A) respectively weighing chlorinated polyethylene elastomer, polyurethane elastomer, glass fiber, ethylene propylene diene monomer, bismuth carboxylate and carbon fluoride according to parts by weight, uniformly mixing, heating and reacting in a reaction furnace at the temperature of 150 ℃, keeping for 8 hours, taking out, and cooling to obtain the high-elasticity agent;
(B) respectively weighing PE, PET, graphene, modified carbon nanofiber, a high elasticity agent, an anti-ultraviolet agent, a toughening agent, a compatilizer, an antioxidant and an auxiliary agent according to the parts by weight for later use;
(C) drying PE at 120 deg.C for 3 hr in a forced air drier, and drying PET at 130 deg.C for 4 hr in a forced air drier;
(D) weighing the dried PE and PET, adding the PE and PET into a high-speed mixer, simultaneously adding the graphene, the modified carbon nanofibers, the high elasticity agent, the anti-ultraviolet agent, the toughening agent, the compatilizer, the antioxidant and the auxiliary agent according to the weight ratio, mixing and stirring for 15 minutes to obtain a mixed material;
(E) adding the blend into a double-screw extruder, and carrying out spinning, washing, oiling, curling, drying and cutting post-treatment processes to obtain composite short fibers; wherein the temperature of the screw extruder is 290 ℃, the aperture of a spinneret plate is 60 mu m, the length of a hole capillary is 400 mu m, the stretching ratio of a nozzle is 3.0, the oiling rate of the fiber is 0.4%, the length of an air gap is 150mm, and the spinning speed is 150 m/min.
In this embodiment, the preparation method of the modified carbon nanofibers comprises:
(a) putting the nano carbon fiber into a low-temperature plasma instrument for processing for 80s with the processing power of 220W;
(b) soaking the treated carbon nanofibers in a beaker filled with mixed acid, wherein the mixed acid is composed of concentrated nitric acid and concentrated sulfuric acid with the volume ratio of 4: 1, then placing the beaker on a magnetic stirrer, reacting for 8 hours at normal temperature, washing with deionized water until the washing solution is neutral, and then drying for 24 hours in vacuum at 120 ℃ to obtain acid oxidized carbon nanofibers;
(c) uniformly mixing ethanol and deionized water in a mass ratio of 7:1 to obtain an ethanol aqueous solution, adding a silane coupling agent, fully stirring and uniformly mixing to obtain a silane coupling agent hydrolysate, dispersing acid-oxidized carbon nanofibers in the silane coupling agent hydrolysate, stirring or ultrasonically treating, filtering out fibers, and drying to obtain the modified carbon nanofibers with the silane coupling agent coating.
Comparative example 1:
the difference from example 3 is that graphene was not added, and the rest is the same as example 3.
Comparative example 2:
the difference from example 3 is that modified filamentous nanocarbon was not added, and the other examples are the same as example 3.
Comparative example 3:
the difference from example 3 is that no elastomer was added, and the other examples are the same as example 3.
Comparative example 4:
the difference from example 3 is that no ultraviolet inhibitor is added, and the other is the same as example 3.
The PE/PET composite elastic staple fibers obtained in examples 2 to 4 and comparative examples 1 to 4 according to the present invention and the conventional composite staple fibers prepared by the conventional formulation process were subjected to performance tests, and the composite staple fibers were made into a through-air non-woven fabric by a through-air bonding process, and the related technical indexes thereof were tested, and the test results are shown in table 1.
The hot air non-woven fabric prepared by the hot air bonding process is subjected to an anti-aging test, the breaking strength retention rate of the hot air non-woven fabric after being irradiated by an ultraviolet lamp for 100 hours is tested, and the breaking strength before and after washing is tested according to GB/T24218.3-2010.
TABLE 1
From the analysis of the above table, the composite fiber prepared by the method disclosed by the invention has the advantages of strong antibacterial property, strong ultraviolet resistance, high elasticity, excellent mechanical property and the like by selecting the raw material composition, optimizing the content of each raw material and selecting the PE, PET, graphene, modified carbon nanofibers, high elasticity agent, ultraviolet resistance agent, toughening agent, compatilizer, antioxidant and auxiliary agent in proper proportion, so that the advantages of each raw material are fully exerted, mutually supplemented and mutually promoted.
From the analysis of the table above, it can be seen that graphene with a proper proportion is added to the composite fiber of the present invention, and the graphene is matched with other components to achieve a good synergistic effect, so that the flexibility and the tensile strength of the composite fiber can be increased.
From the analysis of the above table, it can be seen that the modified carbon nanofibers with appropriate proportions are added to the composite fibers of the present invention, and the modified carbon nanofibers are matched with other components to achieve a good synergistic effect, which is helpful for improving the mechanical properties of the composite fibers, and the breaking strength of the composite fibers is significantly improved compared with that of the uncoated modified carbon nanofibers.
From the analysis of the table above, the composite fiber of the invention is added with the high elasticity agent in a proper proportion, and the raw material composition of the composite fiber is optimized to be matched with other components, so that the composite fiber has good synergistic effect, the elasticity of the composite fiber is effectively improved, and the composite fiber is soft and comfortable in hand feeling.
From the analysis of the above table, it can be seen that the anti-ultraviolet agent is added into the composite fiber in a proper proportion, and the anti-ultraviolet agent is matched with other components to play a good synergistic effect, so that the composite fiber prepared by the invention has excellent aging resistance, and still has a good anti-ultraviolet function after being washed for many times.
In conclusion, the anti-ultraviolet enhanced PE/PET composite elastic short fiber has good performance in all aspects, is remarkably improved, and can greatly meet the market demand.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (10)
1. An anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber is characterized by comprising the following raw materials in parts by weight: 30-50 parts of PE, 30-50 parts of PET, 8-15 parts of graphene, 10-18 parts of modified carbon nanofiber, 8-15 parts of a high elasticity agent, 6-10 parts of an anti-ultraviolet agent, 5-10 parts of a toughening agent, 3-8 parts of a compatilizer, 2-5 parts of an antioxidant and 0.1-2.5 parts of other additives.
2. The UV resistant reinforced PE/PET composite elastic staple fiber according to claim 1, wherein the intrinsic viscosity of the PE is 0.7 to 1.1dl/g, and the intrinsic viscosity of the PET is 0.5 to 1.2 dl/g.
3. The anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber according to claim 1, wherein the high elastic agent is composed of the following raw materials in parts by weight: 40-50 parts of chlorinated polyethylene elastomer, 20-28 parts of polyurethane elastomer, 3-5 parts of glass fiber, 5-10 parts of ethylene propylene diene monomer, 1-2 parts of bismuth carboxylate and 5-7 parts of carbon fluoride.
4. The anti-ultraviolet enhanced PE/PET composite elastic short fiber according to claim 1, wherein the anti-ultraviolet agent is a compound of zinc oxide, titanium dioxide and aluminum oxide in a mass ratio of 1:1:1.5, wherein the average particle size of the zinc oxide is 200-350 nm, the average particle size of the titanium dioxide is 300-400 nm, and the average particle size of the aluminum oxide is 250-500 nm.
5. The UV-resistant enhanced PE/PET composite elastic staple fiber according to claim 1, wherein the compatibilizer is one or more of PE-g-ST, EPDM-g-GMA, ABS-g-MAH, POE-g-MAH and PP-g-MAH.
6. The anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber according to claim 1, wherein the toughening agent is one or more of a styrene-butadiene thermoplastic elastomer, a carboxyl-terminated liquid nitrile rubber, a methyl methacrylate-butadiene-styrene terpolymer and a maleic anhydride grafted polyolefin elastomer, and the grafting ratio of maleic anhydride is 5-25%.
7. The anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber according to claim 1, wherein the antioxidant is a compound of a hindered amine antioxidant, a hindered phenol antioxidant and a phosphite antioxidant in a mass ratio of 1:2: 1.
8. The ultraviolet resistant reinforced grade PE/PET composite elastic staple fiber according to claim 1, wherein the auxiliaries comprise nucleating agents and lubricants; the nucleating agent is one or more of talcum powder, nano silicon dioxide, nano montmorillonite, sodium bicarbonate and sodium benzoate, and the lubricant is one or more of zinc stearate, calcium stearate, pentaerythritol stearate and silicone powder.
9. A process for preparing an anti-uv enhanced grade PE/PET composite elastic staple fiber according to any one of claims 1 to 8, comprising the steps of:
(A) respectively weighing chlorinated polyethylene elastomer, polyurethane elastomer, glass fiber, ethylene propylene diene monomer, bismuth carboxylate and carbon fluoride according to parts by weight, uniformly mixing, heating and reacting in a reaction furnace at the temperature of 140-150 ℃ for 5-8 h, taking out, and cooling to obtain the high-elasticity agent;
(B) respectively weighing PE, PET, graphene, modified carbon nanofiber, a high elasticity agent, an anti-ultraviolet agent, a toughening agent, a compatilizer, an antioxidant and an auxiliary agent according to the parts by weight for later use;
(C) drying PE in a blast drier for 1-3 hours at the temperature of 110-120 ℃, and drying PET in the blast drier for 2-4 hours at the temperature of 115-130 ℃ for later use;
(D) weighing the dried PE and PET, adding the PE and PET into a high-speed mixer, adding the graphene, the modified carbon nanofibers, the high-elasticity agent, the anti-ultraviolet agent, the toughening agent, the compatilizer, the antioxidant and the auxiliary agent according to the weight ratio, mixing and stirring for 5-15 minutes to obtain a mixed material;
(E) adding the blend into a double-screw extruder, and carrying out spinning, washing, oiling, curling, drying and cutting post-treatment processes to obtain composite short fibers; wherein the temperature of the screw extruder is 150-290 ℃, the aperture of a spinneret plate is 10-60 mu m, the length of a hole capillary is 400-600 mu m, the stretching ratio of a spray head is 2.6-3.0, the oiling rate of fibers is 0.3-0.4%, the length of an air gap is 50-200 mm, and the spinning speed is 150-180 m/min.
10. The method for preparing the anti-ultraviolet enhanced-grade PE/PET composite elastic short fiber according to claim 9, wherein the modified nano carbon fiber is prepared by the following steps:
(a) putting the carbon nanofibers into a low-temperature plasma instrument for processing for 25-100 s, wherein the processing power is 120-280W;
(b) soaking the treated carbon nanofibers in a beaker filled with mixed acid, wherein the mixed acid is composed of concentrated nitric acid and concentrated sulfuric acid in a volume ratio of (3-5) to 1, then placing the beaker on a magnetic stirrer, reacting at normal temperature for 6-10 h, washing with deionized water until washing liquor is neutral, and then drying in vacuum at 100-120 ℃ for 24h to obtain acid oxidized carbon nanofibers;
uniformly mixing ethanol and deionized water in a mass ratio of (5-8): 1 to obtain an ethanol aqueous solution, adding a silane coupling agent, fully stirring and uniformly mixing to obtain a silane coupling agent hydrolysate, dispersing the acid oxidized carbon nanofibers in the silane coupling agent hydrolysate, stirring or ultrasonically filtering out fibers, and drying to obtain the modified carbon nanofibers with the silane coupling agent coating.
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