CN113026136A - Polyethylene fiber for automobile sun-proof protective sleeve and preparation method thereof - Google Patents
Polyethylene fiber for automobile sun-proof protective sleeve and preparation method thereof Download PDFInfo
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- CN113026136A CN113026136A CN202110298788.9A CN202110298788A CN113026136A CN 113026136 A CN113026136 A CN 113026136A CN 202110298788 A CN202110298788 A CN 202110298788A CN 113026136 A CN113026136 A CN 113026136A
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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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
Abstract
The invention provides a polyethylene fiber for an automobile sun-proof protective sleeve and a preparation method thereof. The polyethylene fiber comprises the following raw materials in percentage by mass: polyethylene ═ 10-20: 100. the polyethylene fiber can effectively isolate external heat, and is particularly suitable for processing and manufacturing automobile sun-proof protective sleeves.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polyethylene fiber for an automobile sun-proof protective sleeve and a preparation method thereof.
Background
Polyethylene Fiber (English full name: Polyethylene Fiber) refers to a Fiber material obtained by spinning Polyethylene through a melt spinning method, and comprises short fibers and long fibers, the mechanical strength of the Fiber can be adjusted through spinning process parameters, and the Polyethylene Fiber has the advantages of high strength, low density, good insulation and the like, and has wide application prospect in the field of manufacturing of civil products, particularly textiles.
For example, the polyethylene fiber can be used for processing and manufacturing the automobile sun protection sleeve. When the automobile sun-proof protective sleeve is made of the polyethylene fibers, the isolation performance of the polyethylene fibers to external heat is improved, and the automobile sun-proof protective sleeve is very necessary.
Disclosure of Invention
The present invention is aimed at solving at least one of the above-mentioned technical problems, so as to obtain polyethylene fiber suitable for processing and manufacturing automobile sun-protection protective sleeves.
In order to achieve the first object of the present invention, an embodiment of the present invention provides a polyethylene fiber for an automobile sunscreen protective cover, the polyethylene fiber comprises the following raw materials by mass: polyethylene ═ 10-20: 100.
further, the sunscreen additive comprises a phase change thermoregulation material.
Further, the sunscreen additive includes titanium oxide.
To achieve the second object of the present invention, an embodiment of the present invention provides a method for preparing a polyethylene fiber for a protective cover for protecting an automobile from sun light, including:
s100, adding a sun-screening additive: polyethylene ═ 10-20: 100, and preparing the polyethylene fiber by adopting raw materials comprising the sun-screening additive and polyethylene.
Further, S100 includes:
s101, adding a sun-screening additive: polyethylene ═ 10-20: 100, feeding the raw materials comprising the sun-screening additive and polyethylene into a screw melt extrusion device, melting, mixing and extruding;
s102, feeding the material extruded by the screw rod melting extrusion equipment into spinning equipment for spinning to obtain semi-finished fibers;
s103, drawing and winding the semi-finished fiber sprayed by the spinning equipment to obtain the polyethylene fiber.
Further, the sunscreen additive comprises a phase change thermoregulation material.
Further, the sunscreen additive includes titanium oxide.
Further, the sunscreen additive is prepared by the following steps:
s201, weighing 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane, 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane, paraffin and ethylene glycol monobutyl ether, heating, stirring and mixing to obtain a first mixture;
s202, weighing the first mixture, triethanolamine, polysorbate, sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether and water, and ultrasonically emulsifying to obtain a second mixture;
s203, weighing sodium hexametaphosphate, ytterbium nitrate, lanthanum nitrate, titanium oxide, polyvinyl alcohol, acetone and water, and performing ultrasonic dispersion uniformly to obtain a suspension;
s204, dropwise adding ammonia water into the suspension, stirring until the pH value of the suspension reaches 10-11, aging, filtering, washing and drying to obtain a third mixture;
s205, weighing the third mixture, the carbon nano tube, the melamine, the formaldehyde and the water, stirring, mixing, heating, and adjusting the pH value to 8-9 to obtain a fourth mixture;
s206, adjusting the pH value of the second mixture to 5-6, heating and preserving heat, dropwise adding the fourth mixture into the second mixture, stirring, preserving heat and standing after dropwise adding, stopping preserving heat and cooling, adjusting the pH value to 7-8, filtering, washing and drying to obtain the sunscreen additive.
Further, the sunscreen additive is prepared by the following steps:
s301, preparing 2, 2-bis (4-hydroxyphenyl) propane: 1, 3-dimethyl-6-diethylaminofluorane: 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluoran: paraffin wax: ethylene glycol monobutyl ether ═ 1-2: (0.5-1): (0.5-1): 40: weighing 100 mass percent of the materials, and stirring and mixing for 1h to 1.5h at the temperature of 70 ℃ to 80 ℃ to obtain a first mixture;
s302, according to the first mixture: triethanolamine: polysorbate: sorbitan fatty acid ester: fatty alcohol polyoxyethylene ether: water ═ 20-30: (5-10): (5-10): (30-40): (30-40): weighing the materials according to the mass ratio of 100, and performing ultrasonic emulsification for 1 to 1.5 hours to obtain a second mixture;
s303, adding sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: titanium oxide: polyvinyl alcohol: acetone: water ═ 1-1.5: (2-2.5): (20-25): (25-30): (30-35): (30-35): weighing 100 mass percent of the materials, and uniformly dispersing by ultrasonic to obtain a suspension;
s304, dropwise adding ammonia water into the suspension, stirring until the pH value of the suspension reaches 10-11, aging for 1-1.5 h, filtering, washing, and drying to obtain a third mixture;
s305. according to a third mixture: carbon nanotube: melamine: formaldehyde: water ═ 5-10: (5-10): (40-45): (80-90): weighing 100 parts by mass, stirring, mixing, heating to 60-70 ℃, and adjusting the pH value to 8-9 to obtain a fourth mixture;
s306, adjusting the pH value of the second mixture to 5-6, heating to 55-60 ℃, preserving heat, dropwise adding the fourth mixture into the second mixture, stirring, preserving heat, standing for 1-1.5 hours after dropwise adding, stopping preserving heat, cooling, adjusting the pH value to 7-8, filtering, washing and drying to obtain the sunscreen additive, wherein the dropwise adding mass of the fourth mixture is 80-120% of the adding mass of the paraffin.
The beneficial effects of the invention are as follows. The invention adopts the raw materials comprising the sun-proof additive and polyethylene to prepare the polyethylene fiber, the polyethylene fiber has better isolation performance to external heat, and the polyethylene fiber is suitable for processing and manufacturing the automobile sun-proof protective sleeve.
Drawings
FIG. 1 is a graph showing an emission spectrum (excitation wavelength: 365nm) of a modified titanium oxide prepared in example 1 of the present invention.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.
The embodiment provides a polyethylene fiber for an automobile sun-proof protective sleeve, the raw materials of the polyethylene fiber comprise a sun-proof additive and polyethylene, and the mass ratio of the sun-proof additive to the polyethylene is that the sun-proof additive: polyethylene ═ 10-20: 100.
the polyethylene fiber is particularly suitable for processing and manufacturing the automobile sun-proof protective sleeve. The automobile sun-proof protective sleeve covers an automobile, is used for protecting the automobile from being damaged by high temperature in a high-temperature environment in summer, and is particularly widely applied to household small automobiles.
Automotive sun protection covers are typically made from a polymer fiber textile. In order to improve the sun-screening and heat-insulating effects, heat-insulating or sun-screening components need to be added to the polymer fibers used for manufacturing the sun-screening protective cover of the automobile. Therefore, the embodiment of the invention adds the sun-screening additive into the raw materials of the polyethylene fiber to improve the sun-screening, light-resisting and heat-resisting properties of the polyethylene fiber.
Optionally, the sunscreen additive comprises a phase change thermoregulating material. The phase-change temperature-regulating material can be a phase-change temperature-regulating microcapsule material. When the temperature of the outside changes, the phase-change temperature-adjusting material absorbs or releases heat through phase change so as to achieve the purposes of storing energy and heat and adjusting the temperature of the material. By adding the phase-change temperature-regulating material into the sun-screening additive, the polyethylene fiber automobile sun-screening protective sleeve prepared by the embodiment of the invention can absorb heat through phase change in the sun or in a high-temperature environment so as to avoid overhigh temperature on the surface and/or inside of the automobile sun-screening protective sleeve, thereby effectively protecting the automobile.
Optionally, the sunscreen additive comprises titanium oxide. Titanium oxide (i.e. titanium dioxide, TiO)2) As an effective physical sun-screening material, the UV-light in UVB wave band can be effectively blocked. Therefore, the invention can effectively improve the ultraviolet light isolation and resistance performance of the polyethylene.
The embodiment also provides a preparation method of the polyethylene fiber for the automobile sun-proof protective sleeve, which comprises the following steps:
s100, adding a sun-screening additive: polyethylene ═ 10-20: 100, and preparing the polyethylene fiber by adopting raw materials comprising the sun-screening additive and polyethylene.
In some embodiments of this embodiment, S100 includes:
s101, adding a sun-screening additive: polyethylene ═ 10-20: 100, feeding the raw materials comprising the sun-screening additive and polyethylene into a screw melt extrusion device, melting, mixing and extruding;
s102, feeding the material extruded by the screw rod melting extrusion equipment into spinning equipment for spinning to obtain semi-finished fibers;
s103, drawing and winding the semi-finished fiber sprayed by the spinning equipment to obtain the polyethylene fiber.
In some embodiments of this example, the polyethylene is ultra-high molecular weight polyethylene, and the ultra-high molecular weight polyethylene has a molecular weight of 400 to 600 ten thousand.
In some embodiments of this embodiment, other additives or raw materials such as an antioxidant, a coupling agent, a colorant, a dispersant, a solvent, and the like may be added in step S101.
In some embodiments of this embodiment, a decalin solvent may be further added, and the mass ratio of the polyethylene to the decalin solvent is 100: (500-800).
In some embodiments of this example, the screw melt extrusion apparatus has three temperature zones within the apparatus, including an input zone having a temperature in the range of 220 ℃ to 230 ℃, an intermediate zone having a temperature in the range of 240 ℃ to 260 ℃, an output zone having a temperature in the range of 260 ℃ to 280 ℃, and an output head of the screw melt extrusion apparatus having a temperature in the range of 280 ℃ to 300 ℃.
In some embodiments of this embodiment, the draft is a multi-stage draft including a primary draft, a secondary draft, and a tertiary draft, and the draft multiple of the primary draft is 3 times, the draft multiple of the secondary draft is 2 times, and the draft multiple of the tertiary draft is 1.5 times.
In some embodiments of this example, the raw material is subjected to a defoaming process before S101 is executed.
In some embodiments of this example, the spinning process of S102 is performed by a spinning manifold and a metering pump.
In some embodiments of this example, after spinning, the filaments obtained from the spinning process may be extracted and dried.
In some embodiments of this example, the draw of S103 is a multi-stage hot draw of no more than 150 ℃.
In some embodiments of this example, a sunscreen additive is prepared by:
s201, weighing 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane, 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane, paraffin and ethylene glycol monobutyl ether, heating, stirring and mixing to obtain a first mixture;
s202, weighing the first mixture, triethanolamine, polysorbate, sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether and water, and ultrasonically emulsifying to obtain a second mixture;
s203, weighing sodium hexametaphosphate, ytterbium nitrate, lanthanum nitrate, titanium oxide, polyvinyl alcohol, acetone and water, and performing ultrasonic dispersion uniformly to obtain a suspension;
s204, dropwise adding ammonia water into the suspension, stirring until the pH value of the suspension reaches 10-11, aging, filtering, washing and drying to obtain a third mixture;
s205, weighing the third mixture, the carbon nano tube, the melamine, the formaldehyde and the water, stirring, mixing, heating, and adjusting the pH value to 8-9 to obtain a fourth mixture;
s206, adjusting the pH value of the second mixture to 5-6, heating and preserving heat, dropwise adding the fourth mixture into the second mixture, stirring, preserving heat and standing after dropwise adding, stopping preserving heat and cooling, adjusting the pH value to 7-8, filtering, washing and drying to obtain the sunscreen additive.
In some embodiments of this example, a sunscreen additive is prepared by:
s301, preparing 2, 2-bis (4-hydroxyphenyl) propane: 1, 3-dimethyl-6-diethylaminofluorane: 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluoran: paraffin wax: ethylene glycol monobutyl ether ═ 1-2: (0.5-1): (0.5-1): 40: weighing 100 mass percent of the materials, and stirring and mixing for 1h to 1.5h at the temperature of 70 ℃ to 80 ℃ to obtain a first mixture;
s302, according to the first mixture: triethanolamine: polysorbate: sorbitan fatty acid ester: fatty alcohol polyoxyethylene ether: water ═ 20-30: (5-10): (5-10): (30-40): (30-40): weighing the materials according to the mass ratio of 100, and performing ultrasonic emulsification for 1 to 1.5 hours to obtain a second mixture;
s303, adding sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: titanium oxide: polyvinyl alcohol: acetone: water ═ 1-1.5: (2-2.5): (20-25): (25-30): (30-35): (30-35): weighing 100 mass percent of the materials, and uniformly dispersing by ultrasonic to obtain a suspension;
s304, dropwise adding ammonia water into the suspension, stirring until the pH value of the suspension reaches 10-11, aging for 1-1.5 h, filtering, washing, and drying to obtain a third mixture;
s305. according to a third mixture: carbon nanotube: melamine: formaldehyde: water ═ 5-10: (5-10): (40-45): (80-90): weighing 100 parts by mass, stirring, mixing, heating to 60-70 ℃, and adjusting the pH value to 8-9 to obtain a fourth mixture;
s306, adjusting the pH value of the second mixture to 5-6, heating to 55-60 ℃, preserving heat, dropwise adding the fourth mixture into the second mixture, stirring, preserving heat, standing for 1-1.5 hours after dropwise adding, stopping preserving heat, cooling, adjusting the pH value to 7-8, filtering, washing and drying to obtain the sunscreen additive, wherein the dropwise adding mass of the fourth mixture is 80-120% of the adding mass of the paraffin.
In the above embodiments, S301 to S306 provide a preparation method of the sunscreen additive for incorporation into polyethylene. The reason why the sunscreen additive is prepared by the above-described S301 to S306 in the present embodiment is as follows. In order to improve the thermal insulation performance of the polyethylene fibers, the phase change temperature regulating material is prepared in the embodiment of the invention through S301 to S306. The phase change temperature regulating material can be in the form of microcapsules. The phase-change temperature-regulating material takes a phase-change material as a core material, takes an organic polymer as a wall material, and the organic polymer wall material is coated outside the phase-change material core material. The core material in the above embodiment is paraffin. The paraffin is a phase change energy storage material with stable performance and low cost. Specifically, in the above embodiment, paraffin is used as a raw material, and the second mixture is obtained by mixing and ultrasonically emulsifying the raw material including paraffin, triethanolamine, polysorbate, sorbitan fatty acid ester, fatty alcohol polyoxyethylene ether, and water, where the second mixture is an emulsion of paraffin. Further, the above embodiment uses raw materials including melamine and formaldehyde to prepare a fourth mixture, and the fourth mixture is an organic prepolymer. By dropping the fourth mixture into the second mixture and stirring it continuously, the organic prepolymer can be polymerized to form a film on the surface of the core material including paraffin to form a wall material. Thus, a phase change temperature control material (also referred to as a heat storage temperature control material) can be formed by wrapping a polymer wall material around the paraffin core material. For the protective cover for automobile sun protection made of the polyethylene fiber of the embodiment of the invention, when the temperature of the external environment is increased due to the irradiation of sunlight, the paraffin wax core embedded in the wall material generates solid-liquid phase change. In the phase change process, the paraffin absorbs heat and stores heat, so that the temperature of the automobile sun-proof protective sleeve is reduced, and the heat insulation and cooling effects are realized to a certain extent. In addition, in order to further improve the performance of the polyethylene fiber and make the polyethylene fiber more suitable for processing and manufacturing the automobile sun protection sleeve, the core material and the wall material are respectively modified in the embodiment. Specifically, in the above embodiment, before the paraffin emulsion is prepared in S302, the paraffin and 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane, and 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane are uniformly mixed in ethylene glycol monobutyl ether in S301, and the temperature is raised to obtain the first mixture. In S301, ethylene glycol monobutyl ether is used as the organic solvent, 2, 2-bis (4-hydroxyphenyl) propane is used as the coloring material, and 1, 3-dimethyl-6-diethylaminofluorane and 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane are used as the coloring material. 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane and 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane are used as thermochromic dyes, and can endow the paraffin core material with thermochromic performance. The thermochromic properties are: the color of the material can follow the ambient temperature to generate corresponding changing performance. Such as: the material can change the shade of the color tone, the lightness of the color or the color value of the color along with the rise of the external temperature. Due to the addition of 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane and 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane, the paraffin core material according to the example of the present invention exhibited a red or orange-red color at low temperatures (below about 42 ℃) and exhibited no color at high temperatures (above about 42 ℃). Therefore, when the polyethylene fiber provided by the embodiment of the invention is applied to processing and manufacturing of the automobile sun-proof protective sleeve, the automobile sun-proof protective sleeve and the temperature environment of an automobile can be represented through color change, so that a user can determine whether the parking position or parking environment of the automobile needs to be changed according to the real-time temperature condition. And 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane and 2 '-chloro-6' - (diethylamino) -3 '-methylfluorane are mixed with paraffin to form a core material, so that the 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane and 2' -chloro-6 '- (diethylamino) -3' -methylfluorane can be effectively protected by the polymer wall material, and the loss and failure of the polymer wall material due to water washing, high temperature and long-term use can be avoided to a certain extent. In addition, in the embodiment of the present invention, when the fourth mixture including melamine and a performed formaldehyde polymer is prepared through S305, the third mixture and carbon nanotubes are added to the mixture of melamine, formaldehyde and water. The third mixture includes titanium oxide. Titanium oxide and carbon nanotubes are commercially available. It should be noted that although paraffin has many advantages such as high latent heat of phase change, wide range of melting point, stable performance, and low cost. However, the phase-change temperature-regulating material prepared by adopting the paraffin material has the defects of low heat conductivity coefficient and poor light absorption. In other words, the heat conduction efficiency from the outside of the material wall material to the paraffin core material is not ideal, which results in that the phase-change temperature regulation efficiency and effect of the paraffin core material are required to be further improved. In addition, although the paraffin phase-change material can realize the functions of heat storage and energy storage or temperature regulation, the absorption and utilization rate of the paraffin phase-change material on natural illumination still needs to be improved. In order to improve the heat conduction efficiency from the outside of the material wall material to the paraffin core material, the above embodiment adds carbon nanotubes to the sunscreen additive. The carbon nanotubes not only have the advantage of high mechanical strength, but also can be uniformly distributed in the mixture of melamine and formaldehyde and coated on the surface of the paraffin wax core material because the carbon nanotubes are mixed with melamine, formaldehyde and water in the above embodiment. Therefore, the addition of the carbon nano tube can not only improve the strength of the polyethylene fiber, but also enable heat generated on the surface of the polyethylene fiber due to natural light irradiation on the surface of the polyethylene fiber to be effectively transferred into the core material of the material from the surface of the wall material of the material, so that the paraffin wax core material can more efficiently exert a phase change heat absorption effect, for example, the overhigh temperature of the automobile sun-proof protective sleeve can be effectively avoided. In order to improve the absorption and utilization rate of natural light by paraffin, the embodiment adds the photo-thermal conversion component in the preparation process of the sun-screening additive for polyethylene fibers. Raw materials of the photothermal conversion component comprise ytterbium nitrate and lanthanum nitrate. In S303, titanium oxide is dispersed in a mixed solvent of polyvinyl alcohol, acetone, and water as a suspension by the action of sodium hexametaphosphate as a dispersant. Ytterbium nitrate and lanthanum nitrate are dissolved in a mixed solvent of polyvinyl alcohol, acetone and water, thereby trivalent free ytterbium ions and lanthanum ions are obtained. In S304, the pH of the suspension is adjusted to be alkaline by adding alkaline aqueous ammonia (concentration 22% to 28%) dropwise to the suspension. Trivalent free ytterbium ion and lanthanum ion are combined with hydroxyl to form a mixture of ytterbium hydroxide and lanthanum hydroxide, and the mixture is deposited and coated on the surface of the titanium oxide. Therefore, in S304, after filtering, washing, and drying, the third mixture is obtained as a powder on which the modified titanium oxide coated with ytterbium hydroxide and lanthanum hydroxide is deposited. In S305, the modified titanium oxide is mixed with melamine, formaldehyde and water, so that the modified titanium oxide can be uniformly distributed in the mixture of melamine and formaldehyde and coated on the surface of the paraffin wax core. In order to improve the uniformity of the distribution of the modified titanium oxide in the mixture of melamine and formaldehyde, sodium hexametaphosphate dispersant or surfactant such as sodium dodecyl benzene sulfonate can be added into S305 in an amount of 1-2% by mass of the third mixture. FIG. 1 is a graph showing an emission spectrum (excitation wavelength: 365nm) of a modified titanium oxide prepared in example 1 of the present invention. Since the surface of the modified titanium oxide prepared in example 1 is deposited and coated with a mixture of ytterbium hydroxide and lanthanum hydroxide, under the excitation of ultraviolet light, the rare earth ions ytterbium and lanthanum undergo energy level transition in a 5d4f configuration, absorb ultraviolet light energy and emit broadband infrared light having a wavelength range of 980nm to 1100nm by down conversion (down conversion). Therefore, the addition of the modified titanium oxide can not only improve the uvioresistant performance of the polyethylene fiber, but also convert the light energy of the medium-long wave ultraviolet band irradiated by natural light into infrared light energy. Compared with ultraviolet light energy, infrared light energy has obvious thermal effect. Thus, the polymer wall material including the modified titanium oxide can absorb ultraviolet light energy and convert the ultraviolet light energy into infrared light energy, which can be absorbed through phase transition of the paraffin core material. The embodiment can not only improve the ultraviolet absorption performance of the polyethylene fiber, but also improve the absorption and utilization rate of the sunscreen additive of the polyethylene fiber to natural illumination when the phase change absorbs heat.
In some embodiments of this example, a sunscreen additive is prepared by:
s401, according to the weight ratio of 2, 2-bis (4-hydroxyphenyl) propane: 1, 3-dimethyl-6-diethylaminofluorane: 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluoran: ethyl palmitate: ethylene glycol monobutyl ether ═ 1-2: (0.5-1): (0.5-1): 40: weighing 100 parts by mass, and stirring and mixing for 2 to 3 hours at the temperature of between 20 and 40 ℃ to obtain a fifth mixture;
s402, mixing the following materials according to a fifth mixture: triethanolamine: polysorbate: sorbitan fatty acid ester: fatty alcohol polyoxyethylene ether: water ═ 20-30: (5-10): (5-10): (30-40): (30-40): weighing the materials according to the mass ratio of 100, and performing ultrasonic emulsification for 2 to 3 hours to obtain a sixth mixture;
s403, mixing sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: zinc oxide: polyvinyl alcohol: acetone: water ═ 1-1.5: (2-2.5): (20-25): (25-30): (30-35): (30-35): weighing 100 mass percent of the materials, and uniformly dispersing by ultrasonic to obtain a suspension;
s404, adding ammonia water into the suspension dropwise and stirring until the pH value of the suspension reaches 10-11, aging for 1-1.5 h, filtering, washing and drying to obtain a seventh mixture;
s405, mixing the following materials according to a seventh mixture: carbon nanotube: polyethyleneimine: water ═ 5-10: (5-10): (80-90): 100, stirring and mixing at the temperature of 20-40 ℃ to obtain an eighth mixture;
s406, dropwise adding the eighth mixture into the sixth mixture at the temperature of 20-40 ℃ and stirring, keeping the temperature and standing for 1-1.5 hours after dropwise adding, adjusting the pH value to 7-8, filtering, washing and drying to obtain the sun-screening additive, wherein the dropwise adding mass of the eighth mixture is 100-150% of the adding mass of the ethyl palmitate.
The above embodiments provide a method of preparing another sunscreen additive that also includes a phase change thermoregulating material. The phase-change temperature-regulating material does not take paraffin as a core material, but takes Ethyl Palmitate (Ethyl Palmitate) as a core material and takes polyethyleneimine as a wall material. Ethyl palmitate had higher surface activity than paraffin wax, and 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane and 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane were dispersed more uniformly in ethyl palmitate. The molecular weight of the polyethyleneimine used in the above embodiment is 50000 to 80000. While the eighth mixture was added dropwise to the sixth mixture and stirred, polyethyleneimine was coated on the surface of ethyl palmitate containing 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane and 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane by electrostatic adsorption, to form a microcapsule. In addition, the polyethyleneimine belongs to a high-molecular polymer with good water solubility, and the carbon nanotubes and the modified titanium oxide can be uniformly dispersed in a mixed solution of the polyethyleneimine and water, so that the uniform dispersion degree of the carbon nanotubes and the modified titanium oxide on the surface of the core material is improved.
Example 1
This example provides a method for preparing modified titanium oxide. The modified titanium oxide is prepared by the following steps.
S501, adding sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: titanium oxide: polyvinyl alcohol: acetone: water 1: 2: 20: 25: 30: 30: weighing 100 mass percent of the materials and ultrasonically dispersing for 20min to obtain a suspension;
s502, adding 22% ammonia water dropwise into the suspension, stirring until the pH value of the suspension reaches 10, aging for 1h, filtering by using filter paper, washing for 3 times by using deionized water, and performing infrared drying to obtain powdery modified titanium oxide.
Wherein the emission spectrum of the modified titanium oxide prepared in example 1 was measured by a Jobin Yvon Fluorolog-3 fluorescence spectrophotometer using ultraviolet light having an excitation wavelength of 365nm as an excitation light source. The test results are shown in fig. 1. The modified titanium oxide prepared in example 1 emits a broad band infrared light in the wavelength range of 980nm to 1100nm under the excitation of ultraviolet light.
Example 2
This example provides a method for preparing a sunscreen additive, as follows.
S601. adding 2, 2-bis (4-hydroxyphenyl) propane: 1, 3-dimethyl-6-diethylaminofluorane: 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluoran: paraffin wax: ethylene glycol monobutyl ether 1: 0.5: 0.5: 40: weighing 100 parts by mass, and stirring and mixing for 1h at the temperature of 70 ℃ to obtain a first mixture;
s602, according to the first mixture: triethanolamine: polysorbate: sorbitan fatty acid ester: fatty alcohol polyoxyethylene ether: 20 parts of water: 5: 5: 30: 30: weighing the materials according to the mass ratio of 100, and performing ultrasonic emulsification for 1h to obtain a second mixture;
s603, adding sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: titanium oxide: polyvinyl alcohol: acetone: water 1: 2: 20: 25: 30: 30: weighing 100 mass percent of the materials, and uniformly dispersing for 20min by ultrasonic to obtain a suspension;
s604, dropwise adding 22% ammonia water into the suspension, stirring until the pH value of the suspension reaches 10, aging for 1h, filtering by using filter paper, washing for 3 times by using deionized water, and performing infrared drying to obtain a third mixture; wherein the preparation process of the third mixture is the same as that of the embodiment 1, and the third mixture is the modified titanium oxide;
s605, according to a third mixture: carbon nanotube: melamine: formaldehyde: water 5: 5: 40: 80: weighing 100 parts by mass, stirring, mixing, heating to 60 ℃, and adjusting the pH value to 8-9 to obtain a fourth mixture; wherein, the concentration of formaldehyde is 37 percent;
s606, adjusting the pH value of the second mixture to 5, heating to 55 ℃ and preserving heat, dropwise adding the fourth mixture into the second mixture and stirring, preserving heat and standing for 1 hour after dropwise adding, stopping preserving heat and cooling, adjusting the pH value to 7, filtering, washing and drying to obtain the sunscreen additive, wherein the dropwise adding mass of the fourth mixture is 80% of the adding mass of the paraffin.
Example 3
This example provides a method for preparing a sunscreen additive, as follows.
S701, preparing a 2, 2-bis (4-hydroxyphenyl) propane: 1, 3-dimethyl-6-diethylaminofluorane: 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluoran: paraffin wax: ethylene glycol monobutyl ether 2: 1: 1: 40: weighing 100 parts by mass, and stirring and mixing for 1.5 hours at the temperature of 80 ℃ to obtain a first mixture;
s702, according to the first mixture: triethanolamine: polysorbate: sorbitan fatty acid ester: fatty alcohol polyoxyethylene ether: water 30: 10: 10: 40: 40: weighing the materials according to the mass ratio of 100, and performing ultrasonic emulsification for 1.5h to obtain a second mixture;
s703, adding sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: titanium oxide: polyvinyl alcohol: acetone: water 1.5: 2.5: 25: 30: 35: 35: weighing 100 mass percent of the materials, and uniformly dispersing for 40min by ultrasonic to obtain a suspension;
s704, dropwise adding 25% ammonia water into the suspension, stirring until the pH value of the suspension reaches 11, aging for 1.5h, filtering by using filter paper, washing for 3 times by using deionized water, and performing infrared drying to obtain a third mixture; wherein the third mixture is modified titanium oxide;
s705, according to a third mixture: carbon nanotube: melamine: formaldehyde: water 10: 10: 45: 90: weighing 100 parts by mass of the materials, stirring, mixing, heating to 70 ℃, and adjusting the pH value to 9 to obtain a fourth mixture; wherein, the concentration of formaldehyde is 37 percent;
s706, adjusting the pH value of the second mixture to 6, heating to 60 ℃ and preserving heat, dropwise adding the fourth mixture into the second mixture and stirring, preserving heat and standing for 1.5 hours after dropwise adding, stopping preserving heat and cooling, adjusting the pH value to 8, filtering, washing and drying to obtain the sunscreen additive, wherein the dropwise adding mass of the fourth mixture is 120% of the adding mass of the paraffin.
Example 4
This example provides a method for preparing a sunscreen additive, as follows.
S801. adding 2, 2-bis (4-hydroxyphenyl) propane: 1, 3-dimethyl-6-diethylaminofluorane: 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluoran: ethyl palmitate: ethylene glycol monobutyl ether 1: 0.5: 0.5: 40: weighing 100 parts by mass, and stirring and mixing for 2 hours at the temperature of 20 ℃ to obtain a fifth mixture;
s802, according to a fifth mixture: triethanolamine: polysorbate: sorbitan fatty acid ester: fatty alcohol polyoxyethylene ether: 20 parts of water: 5: 5: 30: 30: weighing the materials according to the mass ratio of 100, and performing ultrasonic emulsification for 2 hours to obtain a sixth mixture;
s803. adding sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: zinc oxide: polyvinyl alcohol: acetone: water 1: 2: 20: 25: 30: 30: weighing 100 mass percent of the materials, and uniformly dispersing by ultrasonic to obtain a suspension;
s804, adding ammonia water into the suspension and stirring until the pH value of the suspension reaches 10, aging for 1h, filtering, washing and drying to obtain a seventh mixture;
s805. according to the seventh mixture: carbon nanotube: polyethyleneimine: water 5: 5: 80: 100, stirring and mixing at the temperature of 20 ℃ to obtain an eighth mixture;
s806, adding the eighth mixture dropwise into the sixth mixture at the temperature of 20 ℃ and stirring, keeping the temperature and standing for 1 hour after the addition, adjusting the pH value to 7, filtering, washing and drying to obtain the sunscreen additive, wherein the adding mass of the eighth mixture is 100% of the adding mass of the ethyl palmitate.
Example 5
This example provides a method for preparing a sunscreen additive, as follows.
S801. adding 2, 2-bis (4-hydroxyphenyl) propane: 1, 3-dimethyl-6-diethylaminofluorane: 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluoran: ethyl palmitate: ethylene glycol monobutyl ether 2: 1: 1: 40: weighing 100 parts by mass, and stirring and mixing for 3 hours at the temperature of 40 ℃ to obtain a fifth mixture;
s802, according to a fifth mixture: triethanolamine: polysorbate: sorbitan fatty acid ester: fatty alcohol polyoxyethylene ether: water 30: 10: 10: 40: 40: weighing the materials according to the mass ratio of 100, and performing ultrasonic emulsification for 3 hours to obtain a sixth mixture;
s803. adding sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: zinc oxide: polyvinyl alcohol: acetone: water 1.5: 2.5: 25: 30: 35: 35: weighing 100 mass percent of the materials, and uniformly dispersing by ultrasonic to obtain a suspension;
s804, adding ammonia water into the suspension and stirring until the pH value of the suspension reaches 11, aging for 1.5h, filtering, washing and drying to obtain a seventh mixture;
s805. according to the seventh mixture: carbon nanotube: polyethyleneimine: water 10: 10: 90: 100, stirring and mixing at the temperature of 40 ℃ to obtain an eighth mixture;
s806, adding the eighth mixture dropwise into the sixth mixture at the temperature of 40 ℃ and stirring, keeping the temperature and standing for 1.5 hours after the addition, adjusting the pH value to 8, filtering, washing and drying to obtain the sunscreen additive, wherein the adding mass of the eighth mixture is 150% of the adding mass of the ethyl palmitate.
Example 6
This example provides a method for preparing polyethylene fibers, as follows.
S901, adding a sun-screening additive: polyethylene 10: 100, feeding the raw materials comprising the sun-screening additive and polyethylene into a screw melt extrusion device, melting, mixing and extruding; wherein, the sunscreen additive adopted in this example is the sunscreen additive prepared in example 2; the molecular weight of the polyethylene used in this example is 400 to 600 ten thousand;
s902, feeding the material extruded by the screw rod melting extrusion equipment into spinning equipment for spinning to obtain semi-finished fibers;
and S903, drafting and winding the semi-finished fiber sprayed by the spinning equipment to obtain the polyethylene fiber.
Example 7
This example provides a method for making polyethylene fibers. The details are as follows.
S1001, adding a sun-screening additive: polyethylene 20: 100, feeding the raw materials comprising the sun-screening additive and polyethylene into a screw melt extrusion device, melting, mixing and extruding; wherein, the sunscreen additive used in this example is the sunscreen additive prepared in example 3; the molecular weight of the polyethylene used in this example is 400 to 600 ten thousand;
s1002, feeding the material extruded by the screw rod melting extrusion equipment into spinning equipment for spinning to obtain semi-finished fibers;
s1003, drawing and winding the semi-finished fiber sprayed by the spinning equipment to obtain the polyethylene fiber.
Performance testing
In order to measure the strength of the polyethylene fibers of the examples of the present invention, the polyethylene fibers obtained in examples 6 and 7 were subjected to mechanical property tests. The strength of the polyethylene fiber of example 6 was 38.2CN/dtex, and the strength of the polyethylene fiber of example 7 was 37.0 CN/dtex.
In order to measure the aging resistance of the polyethylene fibers of the examples of the present invention under the conditions of light and high temperature, the polyethylene fibers prepared in examples 6 and 7 were treated under a 100W xenon lamp light source and a temperature of 80 ℃ for 72 hours, and then the mechanical properties of the polyethylene fibers obtained in examples 6 and 7 were measured again. After the accelerated aging test, the strength of the polyethylene fiber of example 6 was 37.4CN/dtex, and the strength of the polyethylene fiber of example 7 was 36.6 CN/dtex.
In the present invention, the terms "first", "second", and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance; the term "plurality" means two or more unless expressly limited otherwise. The terms "mounted," "connected," "fixed," and the like are to be construed broadly, and for example, "connected" may be a fixed connection, a removable connection, or an integral connection; "coupled" may be direct or indirect through an intermediary. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
In the description herein, the description of the terms "one embodiment," "some embodiments," "specific embodiments," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The polyethylene fiber for the automobile sun-proof protective sleeve is characterized in that raw materials of the polyethylene fiber comprise a sun-proof additive and polyethylene, and the mass ratio of the sun-proof additive to the polyethylene is that the sun-proof additive: polyethylene ═ 10-20: 100.
2. the polyethylene fiber for an automotive sun protection sleeve according to claim 1, wherein the sun protection additive comprises a phase change temperature regulating material.
3. The polyethylene fiber for an automotive sun protection sleeve according to claim 1, wherein the sun protection additive comprises titanium oxide.
4. A preparation method of polyethylene fiber for an automobile sun-proof protective sleeve is characterized by comprising the following steps:
s100, adding a sun-screening additive: polyethylene ═ 10-20: 100, and preparing the polyethylene fiber by adopting raw materials comprising the sun-screening additive and the polyethylene.
5. The method for preparing polyethylene fiber for use in an automobile sun protection sleeve according to claim 4, wherein the S100 comprises:
s101, adding a sun-screening additive: polyethylene ═ 10-20: 100, feeding the raw materials comprising the sunscreen additive and the polyethylene into a screw melt extrusion device, melting, mixing and extruding;
s102, feeding the material extruded by the screw rod melting extrusion equipment into spinning equipment for spinning to obtain semi-finished fibers;
s103, drawing and winding the semi-finished fiber sprayed by the spinning equipment to obtain the polyethylene fiber.
6. The method of making polyethylene fiber for use in an automotive sun protection sleeve according to any one of claims 4 to 5, wherein the sun protection additive comprises a phase change temperature regulating material.
7. The method of making polyethylene fiber for use in an automotive sun protection sleeve according to any one of claims 4 to 5, wherein the sun protection additive comprises titanium oxide.
8. The method of preparing polyethylene fiber for use in an automotive sun protection sleeve according to any one of claims 4 to 5, wherein the sun protection additive is prepared by the steps of:
s201, weighing 2, 2-bis (4-hydroxyphenyl) propane, 1, 3-dimethyl-6-diethylaminofluorane, 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluorane, paraffin and ethylene glycol monobutyl ether, heating, stirring and mixing to obtain a first mixture;
s202, weighing the first mixture, triethanolamine, polysorbate, sorbitan fatty acid ester, fatty alcohol-polyoxyethylene ether and water, and ultrasonically emulsifying to obtain a second mixture;
s203, weighing sodium hexametaphosphate, ytterbium nitrate, lanthanum nitrate, titanium oxide, polyvinyl alcohol, acetone and water, and performing ultrasonic dispersion uniformly to obtain a suspension;
s204, dropwise adding ammonia water into the suspension, stirring until the pH value of the suspension reaches 10-11, aging, filtering, washing and drying to obtain a third mixture;
s205, weighing the third mixture, the carbon nano tube, the melamine, the formaldehyde and the water, stirring, mixing, heating, and adjusting the pH value to 8-9 to obtain a fourth mixture;
s206, adjusting the pH value of the second mixture to 5-6, heating and preserving heat, dropwise adding the fourth mixture into the second mixture, stirring, preserving heat and standing after dropwise adding, stopping preserving heat and cooling, adjusting the pH value to 7-8, filtering, washing and drying to obtain the sunscreen additive.
9. The method of preparing polyethylene fiber for use in an automotive sun protection sleeve according to any one of claims 4 to 5, wherein the sun protection additive is prepared by the steps of:
s301, preparing 2, 2-bis (4-hydroxyphenyl) propane: 1, 3-dimethyl-6-diethylaminofluorane: 2 ' -chloro-6 ' - (diethylamino) -3 ' -methylfluoran: paraffin wax: ethylene glycol monobutyl ether ═ 1-2: (0.5-1): (0.5-1): 40: weighing 100 mass percent of the materials, and stirring and mixing for 1h to 1.5h at the temperature of 70 ℃ to 80 ℃ to obtain a first mixture;
s302, according to the first mixture: triethanolamine: polysorbate: sorbitan fatty acid ester: fatty alcohol polyoxyethylene ether: water ═ 20-30: (5-10): (5-10): (30-40): (30-40): weighing the materials according to the mass ratio of 100, and performing ultrasonic emulsification for 1 to 1.5 hours to obtain a second mixture;
s303, adding sodium hexametaphosphate: ytterbium nitrate: lanthanum nitrate: titanium oxide: polyvinyl alcohol: acetone: water ═ 1-1.5: (2-2.5): (20-25): (25-30): (30-35): (30-35): weighing 100 mass percent of the materials, and uniformly dispersing by ultrasonic to obtain a suspension;
s304, dropwise adding ammonia water into the suspension, stirring until the pH value of the suspension reaches 10-11, aging for 1-1.5 h, filtering, washing, and drying to obtain a third mixture;
s305. according to a third mixture: carbon nanotube: melamine: formaldehyde: water ═ 5-10: (5-10): (40-45): (80-90): weighing 100 parts by mass, stirring, mixing, heating to 60-70 ℃, and adjusting the pH value to 8-9 to obtain a fourth mixture;
s306, adjusting the pH value of the second mixture to 5-6, heating to 55-60 ℃, preserving heat, dropwise adding the fourth mixture into the second mixture, stirring, preserving heat, standing for 1-1.5 hours after dropwise adding, stopping preserving heat, cooling, adjusting the pH value to 7-8, filtering, washing and drying to obtain the sun-screening additive, wherein the dropwise adding mass of the fourth mixture is 80-120% of the adding mass of the paraffin.
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