CN113957716A - Color-changing fiber and manufacturing process thereof - Google Patents
Color-changing fiber and manufacturing process thereof Download PDFInfo
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- 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
- D01F6/52—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 polymers of unsaturated carboxylic acids or unsaturated esters
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- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
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- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a color-changing fiber and a manufacturing process thereof, wherein the color-changing fiber comprises a fiber core and a cladding material wrapped outside the fiber core, and the fiber core comprises the following components in parts by weight: 80-100 parts of polymethyl methacrylate, 3-6 parts of scandium disilicate/cobalt diselenide nano powder and 1.2-3.6 parts of glycidyl methacrylate. The cladding material comprises the following components in parts by weight: 50-80 parts of polyethylene terephthalate, 25-35 parts of unsaturated polyester resin, 11-16 parts of polyurethane acrylate, 5-10 parts of nano cellulose and 6-12 parts of curing agent. According to the invention, the flexible color-changing fiber is constructed by optimally designing the micro-nano structure of the fiber and combining with an advanced manufacturing technology, the fiber has excellent light transmission, is flexible and breathable, can be washed by water, has good durability, and can be used for preparing intelligent wearable fabrics based on the color-changing fiber.
Description
Technical Field
The invention relates to the field of color-changing fibers, in particular to a color-changing fiber and a manufacturing process thereof.
Background
The intelligent fabric type technology of the color-changing fiber is a flexible wearable technology which is humanized and accords with human intuition, is one of the most representative fields of current international leading edge academic research field and global advanced manufacturing technology development. The U.S. government and industry are building "U.S. manufacturing programs" throughout the country, aiming to build the future U.S. advanced manufacturing innovation competitiveness with an investment of $ 3.17 million and $ 1.71 million, respectively, to form the advanced functional fiber and fabric research institute AFFOA, flexible composite electronics research institute NextFlex, etc. Countries such as Japan, European Union, Australia and the like also take future strategic placement in the fields of functional fibers and intelligent textiles. The famous investment institutions, soft silver companies and the like, also make global investment layouts in this field. The key technology and industry of great commonality in this field in the country at present are behind the international advanced developed countries.
Chinese patent CN110257932A discloses a luminescent color-changing monofilament and a preparation method thereof. Melting the polymer matrix raw material, and then adding an additive with the same refractive index as the polymer matrix raw material; and carrying out melt blending and extrusion in a melt extruder, cooling, stretching, heat setting and winding to obtain the color-changing fiber monofilament, and then thermally attaching one end of the color-changing fiber monofilament to an LED lamp strip to obtain the luminous color-changing monofilament. The color-changing fiber monofilament has good light transmission performance, can be used for human wig hair, woven luminous color-developing fabrics, warning boards and the like, light conduction induction control sensing units and the like, but has the defects of low tensile strength, low breaking strength and low surface hardness.
Disclosure of Invention
Aiming at the problems of low luminous efficiency, high optical loss and low strength of the color-changing fiber monofilament used in the prior art, the invention aims to provide a color-changing fiber and a manufacturing process thereof.
The purpose of the invention is realized by adopting the following technical scheme:
in a first aspect, the present invention provides a color-changing fiber, which includes a fiber core and a cladding material wrapped outside the fiber core, wherein the fiber core includes the following components, by weight:
80-100 parts of polymethyl methacrylate, 3-6 parts of scandium disilicate/cobalt diselenide nano powder and 1.2-3.6 parts of glycidyl methacrylate.
The cladding material comprises the following components in parts by weight:
50-80 parts of polyethylene terephthalate, 25-35 parts of unsaturated polyester resin, 11-16 parts of polyurethane acrylate, 5-10 parts of nano cellulose and 6-12 parts of curing agent.
Preferably, the unsaturated polyester resin is prepared by reacting any one of dihydric alcohol, trihydric alcohol and tetrahydric alcohol with dibasic acid.
Preferably, the curing agent is obtained by mixing benzoyl peroxide and glutaraldehyde according to a mass ratio of 2-3: 1.
Preferably, the diameter of the cross section of the fiber core is 20-50 μm, and the thickness of the cladding material is 5-10 μm.
Preferably, the preparation method of the scandium disilicate/cobalt diselenide nano powder comprises the following steps:
s1, weighing cobalt nitrate and sodium selenite, sequentially adding the cobalt nitrate and the sodium selenite into deionized water, stirring until the cobalt nitrate and the sodium selenite are completely dissolved, adding ethylene diamine tetraacetic acid, uniformly mixing, and reacting to obtain nano cobalt diselenide; wherein the mass ratio of the cobalt nitrate to the sodium selenite to the ethylenediamine tetraacetic acid to the deionized water is 1: 1.1-1.3: 5.8-7.2: 2.4-3.6;
s2, weighing scandium oxide, mixing with deionized water, dropwise adding hydrochloric acid, dissolving solids by controlling the reaction temperature, separating out again, continuously stirring for 10-12 h at 20-30 ℃, then carrying out solid-liquid separation on the reaction liquid, washing the separated solids with water, and drying to obtain reaction crystals; wherein the concentration of the hydrochloric acid is 0.1-0.2 mol/L, and the mass ratio of the scandium oxide, the hydrochloric acid and the deionized water is 1: 5-8: 6-12;
s3, weighing ethyl orthosilicate, mixing the ethyl orthosilicate with an ethanol solution with the mass fraction being equal to that of the ethyl orthosilicate, uniformly stirring, adding a reaction crystal, uniformly stirring again, stirring for 4-6 hours at 20-30 ℃, adding nano cobalt diselenide, and continuously stirring for 2-4 hours to obtain a reaction mixture; wherein the mass fraction of the ethanol solution is 20-50%, and the mass ratio of the reaction crystal, the nano cobalt diselenide, the tetraethoxysilane and the ethanol solution is 1: 0.3-0.6: 2.42-2.86: 3-5;
s4, drying the reaction mixture in an oven at 80-100 ℃, crushing into powder, sintering in a high-temperature furnace at 800-1000 ℃ for 5-8 h, and crushing the obtained solid into nano-powder to obtain the scandium disilicate/cobalt diselenide nano-powder.
Preferably, the reaction conditions in S1 are: and (3) uniformly mixing the reaction solution, moving the reaction solution into a reaction kettle with polytetrafluoroethylene as an inner lining, sealing the reaction kettle, placing the reaction kettle in an environment with the temperature of 150-180 ℃, preserving heat for 8-10 hours, filtering out solids, washing with water and drying to obtain the nano cobalt diselenide.
Preferably, in S2, the method of controlling the reaction temperature to dissolve the solid and then precipitate the solid again specifically includes: after the hydrochloric acid is dropwise added, heating to 60-80 ℃, stirring until the hydrochloric acid is completely dissolved, then stopping heating, gradually precipitating solids in the reaction liquid, and continuously stirring until the precipitated solids in the reaction liquid do not increase any more.
In a second aspect, the invention provides a process for manufacturing a color-changing fiber, comprising the following steps:
step 1, preparing a fiber core:
weighing polymethyl methacrylate, scandium disilicate/cobalt diselenide nano powder and glycidyl methacrylate according to parts by weight respectively, putting the weighed materials into a mixing stirrer to be melted and mixed uniformly, and preparing fibers to obtain fiber cores;
step 2, preparing a cladding material:
weighing polyethylene glycol terephthalate, unsaturated polyester resin, polyurethane acrylate and nanocellulose according to parts by weight respectively, and placing the materials in a mixing stirrer to be uniformly mixed to obtain a cladding material;
step 3, preparing color-changing fibers:
and adding the weighed curing agent into the cladding material, uniformly dispersing, injecting into a fiber coating machine, passing the fiber core through the fiber coating machine to coat the cladding material on the surface layer of the fiber core, and drying to obtain the color-changing fiber.
Preferably, in the step 1, the fiber is prepared by spinning the fiber through a melt spinning process; wherein the parameters of the melt spinning process are as follows: the melting temperature is 210-250 ℃, the drafting temperature is 100-120 ℃, and the drafting multiple is 2-5 times.
Preferably, in the step 1, the temperature of the mixer-agitator is set to be 160-180 ℃.
Preferably, in the step 2, the temperature of the mixer-stirrer is set to be 25-100 ℃.
Preferably, in the step 3, the drying temperature is set to be 25-50 ℃, and the humidity is set to be 45-60%.
The invention has the beneficial effects that:
according to the invention, the fiber core taking polymethyl methacrylate as a main material and the cladding material taking polyethylene glycol terephthalate as a main material are used, the flexible color-changing fiber is constructed by the micro-nano structure optimization design of the fiber and combining with an advanced manufacturing technology, the fiber has excellent light transmissibility, is flexible and breathable, can be washed by water, has good durability, and can be used for preparing intelligent wearable fabrics based on the color-changing fiber.
The color-changing fiber prepared by the method comprises an inner fiber core and an outer layer of cladding material, wherein the inner fiber core uses polymethyl methacrylate as a main raw material, the optimization and the improvement are carried out on the basis of the polymethyl methacrylate, scandium disilicate/cobalt diselenide nano powder and glycidyl methacrylate are added, the glycidyl methacrylate is mainly used as an adhesive and a blending agent, the scandium disilicate/cobalt diselenide nano powder is used as a modifier, the fiber core prepared by the three materials has better light transmissibility, and has the advantages of small light loss, high luminous efficiency and uniform light emission, and the mechanical property of the polymethyl methacrylate is also enhanced.
The outer layer of the cladding material is mainly prepared by mixing polyethylene glycol terephthalate, unsaturated polyester resin, polyurethane acrylate and nano-cellulose, and the composite material has good mechanical property, excellent toughness, good solvent resistance and excellent gas, water and oil resistance, and can make up for the defects of insufficient toughness and solvent resistance of a fiber core, thereby better protecting the fiber core.
The scandium disilicate/cobalt diselenide nano powder is prepared by firstly preparing nano cobalt diselenide by using cobalt nitrate and sodium selenite, then recrystallizing scandium oxide and reacting tetraethoxysilane to generate a scandium silicate precursor, adding the nano cobalt diselenide prepared in advance in the process, then drying at 80-100 ℃, and then placing in a high-temperature furnace for high-temperature sintering to finally obtain the scandium disilicate/cobalt diselenide nano powder. Experiments prove that compared with the single cobalt diselenide, the scandium disilicate/cobalt diselenide nano powder has stronger enhancement effect on polymethyl methacrylate.
Detailed Description
For the purpose of more clearly illustrating the present invention and more clearly understanding the technical features, objects and advantages of the present invention, the technical solutions of the present invention will now be described in detail below, but are not to be construed as limiting the implementable scope of the present invention.
Unlike conventional glass fibers, plastic fibers have unique advantages such as low modulus, large diameter, and wide range of refractive indices. However, if the plastic fiber is to replace glass fiber, the defect of light propagation attenuation needs to be overcome, in order to explore a manufacturing means of the luminescent plastic fiber, mechanisms of deformation, phase change and the like of different fiber materials need to be deeply researched, the generality of the forming of different materials in a micro-nano structure is searched, and a regulation and control means of the materials is explored.
According to the invention, scandium disilicate/cobalt diselenide nano powder and polymethyl methacrylate are selected and integrated into the same preform, and then a multi-component melt spinning process is adopted, and the internal structure (controllable from nanometer to micron) spinning of the fiber is accurately controlled in a spinneret plate with a special structure by controlling the component proportion, so that the micro-nano structure of different materials in the same fiber is realized, the function of the fiber is realized, and the ideal light guide fiber is realized by optimizing and screening the materials and optimizing the process parameters.
How the fiber uniformly scatters visible light of different wavelengths during transmission depends on the selection and optimization of the fiber core and cladding materials, and their geometric dimensions. The choice of the fiber material and the design of the fiber structure are closely related to the fiber manufacturing process, and the fiber material and the structure both meet the requirement of light transmission and have to be capable of adapting the fiber forming process of the fiber with proper fluidity in the manufacturing process so that the internal structure of the fiber is not deformed and damaged.
Polymethyl methacrylate is a colorless transparent thermoplastic polymer, not only has very high impact strength, excellent thermal stability, creep resistance, cold resistance, electrical insulation and flame retardance, but also has high transparency, the visible light transmittance is as high as more than 90 percent, and the polymethyl methacrylate is often used for preparing lenses, bulletproof glass, headlamps and the like.
The invention is further described below with reference to the following examples.
Example 1
The color-changing fiber comprises a fiber core and a cladding material wrapped outside the fiber core, wherein the cross-sectional diameter of the fiber core is 35 mu m, and the thickness of the cladding material is 8 mu m;
the fiber core comprises the following components in parts by weight:
90 parts of polymethyl methacrylate, 5 parts of scandium disilicate/cobalt diselenide nano powder and 2.4 parts of glycidyl methacrylate.
The cladding material comprises the following components in parts by weight:
65 parts of polyethylene terephthalate, 30 parts of unsaturated polyester resin, 14 parts of urethane acrylate, 8 parts of nano-cellulose and 10 parts of a curing agent.
Wherein, the unsaturated polyester resin is prepared by the reaction of dihydric alcohol and dibasic acid; the curing agent is obtained by mixing benzoyl peroxide and glutaraldehyde according to the mass ratio of 3: 1.
The preparation method of the scandium disilicate/cobalt diselenide nano powder comprises the following steps:
s1, weighing cobalt nitrate and sodium selenite, sequentially adding the cobalt nitrate and the sodium selenite into deionized water, stirring until the cobalt nitrate and the sodium selenite are completely dissolved, adding ethylene diamine tetraacetic acid, uniformly mixing, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an environment with the temperature of 150-180 ℃, carrying out heat preservation treatment for 8-10 hours, filtering out solids, washing with water, and drying to obtain nano cobalt diselenide; wherein the mass ratio of the cobalt nitrate to the sodium selenite to the ethylenediamine tetraacetic acid to the deionized water is 1:1.2:6.3: 3.2;
s2, weighing scandium oxide, mixing with deionized water, dropwise adding hydrochloric acid, heating to 60-80 ℃, stirring until the scandium oxide is completely dissolved, then stopping heating, gradually separating out solids from the reaction liquid, continuously stirring until the separated solids in the reaction liquid are not increased any more, then continuously stirring for 10-12 hours at 20-30 ℃, then separating the solids from the liquid of the reaction liquid, washing the separated solids with water, and drying to obtain reaction crystals; wherein the concentration of the hydrochloric acid is 0.1mol/L, and the mass ratio of the scandium oxide, the hydrochloric acid and the deionized water is 1:6: 10;
s3, weighing ethyl orthosilicate, mixing the ethyl orthosilicate with an ethanol solution with the mass fraction being equal to that of the ethyl orthosilicate, uniformly stirring, adding a reaction crystal, uniformly stirring again, stirring for 4-6 hours at 20-30 ℃, adding nano cobalt diselenide, and continuously stirring for 2-4 hours to obtain a reaction mixture; wherein the mass fraction of the ethanol solution is 35%, and the mass ratio of the reaction crystal, the nano cobalt diselenide, the tetraethoxysilane and the ethanol solution is 1:0.5:2.64: 4;
s4, drying the reaction mixture in an oven at 80-100 ℃, crushing into powder, sintering in a high-temperature furnace at 950 ℃ for 6 hours, and crushing the obtained solid into nano-powder to obtain the scandium disilicate/cobalt diselenide nano-powder.
The manufacturing process of the color-changing fiber comprises the following steps:
step 1, preparing a fiber core:
weighing polymethyl methacrylate, scandium disilicate/cobalt diselenide nano powder and glycidyl methacrylate according to parts by weight respectively, putting the weighed materials into a mixing stirrer at 170 ℃ for melt mixing uniformly, and then spinning the materials into fibers through a melt spinning process to obtain fiber cores; wherein the parameters of the melt spinning process are as follows: the melting temperature is 230 ℃, the drafting temperature is 110 ℃, and the drafting multiple is 3 times;
step 2, preparing a cladding material:
weighing polyethylene glycol terephthalate, unsaturated polyester resin, polyurethane acrylate and nanocellulose according to parts by weight respectively, and uniformly mixing in a mixing stirrer at 70 ℃ to obtain a cladding material;
step 3, preparing color-changing fibers:
and adding the weighed curing agent into the cladding material, uniformly dispersing, injecting into a fiber coating machine, passing the fiber core through the fiber coating machine to coat the cladding material on the surface layer of the fiber core, and drying at the temperature of 35 ℃ and the humidity of 55% to obtain the color-changing fiber.
Example 2
The color-changing fiber comprises a fiber core and a cladding material wrapped outside the fiber core, wherein the cross-sectional diameter of the fiber core is 20 microns, and the thickness of the cladding material is 5 microns;
the fiber core comprises the following components in parts by weight:
80 parts of polymethyl methacrylate, 6 parts of scandium disilicate/cobalt diselenide nano powder and 1.2 parts of glycidyl methacrylate.
The cladding material comprises the following components in parts by weight:
50 parts of polyethylene terephthalate, 35 parts of unsaturated polyester resin, 11 parts of urethane acrylate, 10 parts of nano-cellulose and 6 parts of a curing agent.
Wherein the unsaturated polyester resin is prepared by the reaction of trihydric alcohol and dibasic acid; the curing agent is obtained by mixing benzoyl peroxide and glutaraldehyde according to the mass ratio of 2: 1.
The preparation method of the scandium disilicate/cobalt diselenide nano powder comprises the following steps:
s1, weighing cobalt nitrate and sodium selenite, sequentially adding the cobalt nitrate and the sodium selenite into deionized water, stirring until the cobalt nitrate and the sodium selenite are completely dissolved, adding ethylene diamine tetraacetic acid, uniformly mixing, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an environment with the temperature of 150-180 ℃, carrying out heat preservation treatment for 8-10 hours, filtering out solids, washing with water, and drying to obtain nano cobalt diselenide; wherein the mass ratio of the cobalt nitrate to the sodium selenite to the ethylenediamine tetraacetic acid to the deionized water is 1:1.1:5.8: 2.4;
s2, weighing scandium oxide, mixing with deionized water, dropwise adding hydrochloric acid, heating to 60-80 ℃, stirring until the scandium oxide is completely dissolved, then stopping heating, gradually separating out solids from the reaction liquid, continuously stirring until the separated solids in the reaction liquid are not increased any more, then continuously stirring for 10-12 hours at 20-30 ℃, then separating the solids from the liquid of the reaction liquid, washing the separated solids with water, and drying to obtain reaction crystals; wherein the concentration of the hydrochloric acid is 0.1mol/L, and the mass ratio of the scandium oxide, the hydrochloric acid and the deionized water is 1:5: 6;
s3, weighing ethyl orthosilicate, mixing the ethyl orthosilicate with an ethanol solution with the mass fraction being equal to that of the ethyl orthosilicate, uniformly stirring, adding a reaction crystal, uniformly stirring again, stirring for 4-6 hours at 20-30 ℃, adding nano cobalt diselenide, and continuously stirring for 2-4 hours to obtain a reaction mixture; wherein the mass fraction of the ethanol solution is 20%, and the mass ratio of the reaction crystal, the nano cobalt diselenide, the tetraethoxysilane and the ethanol solution is 1:0.3:2.42: 3;
s4, drying the reaction mixture in an oven at 80-100 ℃, crushing into powder, sintering in a high-temperature furnace at 800 ℃ for 8 hours, and crushing the obtained solid into nano-powder to obtain the scandium disilicate/cobalt diselenide nano-powder.
The manufacturing process of the color-changing fiber comprises the following steps:
step 1, preparing a fiber core:
weighing polymethyl methacrylate, scandium disilicate/cobalt diselenide nano powder and glycidyl methacrylate according to parts by weight respectively, putting the weighed materials into a mixing stirrer at 160 ℃ for melt mixing, and then spinning the materials into fibers through a melt spinning process to obtain fiber cores; wherein the parameters of the melt spinning process are as follows: the melting temperature is 210 ℃, the drafting temperature is 100 ℃, and the drafting multiple is 2 times;
step 2, preparing a cladding material:
weighing polyethylene glycol terephthalate, unsaturated polyester resin, polyurethane acrylate and nanocellulose according to parts by weight respectively, and uniformly mixing in a mixing stirrer at 25 ℃ to obtain a cladding material;
step 3, preparing color-changing fibers:
and adding the weighed curing agent into the cladding material, uniformly dispersing, injecting into a fiber coating machine, passing the fiber core through the fiber coating machine to coat the cladding material on the surface layer of the fiber core, and drying at the temperature of 25 ℃ and the humidity of 45% to obtain the color-changing fiber.
Example 3
The color-changing fiber comprises a fiber core and a cladding material wrapped outside the fiber core, wherein the cross-sectional diameter of the fiber core is 50 mu m, and the thickness of the cladding material is 10 mu m;
the fiber core comprises the following components in parts by weight:
100 parts of polymethyl methacrylate, 3 parts of scandium disilicate/cobalt diselenide nano powder and 3.6 parts of glycidyl methacrylate.
The cladding material comprises the following components in parts by weight:
80 parts of polyethylene terephthalate, 25 parts of unsaturated polyester resin, 16 parts of urethane acrylate, 5 parts of nano-cellulose and 12 parts of a curing agent.
Wherein the unsaturated polyester resin is prepared by the reaction of tetrahydric alcohol and dibasic acid; the curing agent is obtained by mixing benzoyl peroxide and glutaraldehyde according to the mass ratio of 3: 1.
The preparation method of the scandium disilicate/cobalt diselenide nano powder comprises the following steps:
s1, weighing cobalt nitrate and sodium selenite, sequentially adding the cobalt nitrate and the sodium selenite into deionized water, stirring until the cobalt nitrate and the sodium selenite are completely dissolved, adding ethylene diamine tetraacetic acid, uniformly mixing, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an environment with the temperature of 150-180 ℃, carrying out heat preservation treatment for 8-10 hours, filtering out solids, washing with water, and drying to obtain nano cobalt diselenide; wherein the mass ratio of the cobalt nitrate to the sodium selenite to the ethylenediamine tetraacetic acid to the deionized water is 1:1.3:7.2: 3.6;
s2, weighing scandium oxide, mixing with deionized water, dropwise adding hydrochloric acid, heating to 60-80 ℃, stirring until the scandium oxide is completely dissolved, then stopping heating, gradually separating out solids from the reaction liquid, continuously stirring until the separated solids in the reaction liquid are not increased any more, then continuously stirring for 10-12 hours at 20-30 ℃, then separating the solids from the liquid of the reaction liquid, washing the separated solids with water, and drying to obtain reaction crystals; wherein the concentration of the hydrochloric acid is 0.2mol/L, and the mass ratio of the scandium oxide to the hydrochloric acid to the deionized water is 1:8: 12;
s3, weighing ethyl orthosilicate, mixing the ethyl orthosilicate with an ethanol solution with the mass fraction being equal to that of the ethyl orthosilicate, uniformly stirring, adding a reaction crystal, uniformly stirring again, stirring for 4-6 hours at 20-30 ℃, adding nano cobalt diselenide, and continuously stirring for 2-4 hours to obtain a reaction mixture; wherein the mass fraction of the ethanol solution is 50%, and the mass ratio of the reaction crystal, the nano cobalt diselenide, the tetraethoxysilane and the ethanol solution is 1:0.6:2.86: 5;
s4, drying the reaction mixture in an oven at 80-100 ℃, crushing into powder, sintering in a high-temperature furnace at 1000 ℃ for 5 hours, and crushing the obtained solid into nano-powder to obtain the scandium disilicate/cobalt diselenide nano-powder.
The manufacturing process of the color-changing fiber comprises the following steps:
step 1, preparing a fiber core:
weighing polymethyl methacrylate, scandium disilicate/cobalt diselenide nano powder and glycidyl methacrylate according to parts by weight respectively, putting the weighed materials into a mixing stirrer at 180 ℃ for melt mixing, and then spinning the materials into fibers through a melt spinning process to obtain fiber cores; wherein the parameters of the melt spinning process are as follows: the melting temperature is 250 ℃, the drafting temperature is 120 ℃, and the drafting multiple is 5 times;
step 2, preparing a cladding material:
weighing polyethylene glycol terephthalate, unsaturated polyester resin, polyurethane acrylate and nanocellulose according to parts by weight respectively, and uniformly mixing in a mixing stirrer at 100 ℃ to obtain a cladding material;
step 3, preparing color-changing fibers:
and adding the weighed curing agent into the cladding material, uniformly dispersing, injecting into a fiber coating machine, passing the fiber core through the fiber coating machine to coat the cladding material on the surface layer of the fiber core, and drying at the temperature of 50 ℃ and the humidity of 60% to obtain the color-changing fiber.
Comparative example 1
The color-changing fiber comprises a fiber core and a cladding material wrapped outside the fiber core, wherein the cross-sectional diameter of the fiber core is 35 mu m, and the thickness of the cladding material is 8 mu m;
the fiber core comprises the following components in parts by weight:
90 parts of polymethyl methacrylate, 5 parts of cobalt diselenide nano powder and 2.4 parts of glycidyl methacrylate.
The cladding material comprises the following components in parts by weight:
65 parts of polyethylene terephthalate, 30 parts of unsaturated polyester resin, 14 parts of urethane acrylate, 8 parts of nano-cellulose and 10 parts of a curing agent.
Wherein, the unsaturated polyester resin is prepared by the reaction of dihydric alcohol and dibasic acid; the curing agent is obtained by mixing benzoyl peroxide and glutaraldehyde according to the mass ratio of 3: 1.
The preparation method of the cobalt diselenide nano powder comprises the following steps:
s1, weighing cobalt nitrate and sodium selenite, sequentially adding the cobalt nitrate and the sodium selenite into deionized water, stirring until the cobalt nitrate and the sodium selenite are completely dissolved, adding ethylene diamine tetraacetic acid, uniformly mixing, transferring the mixture into a reaction kettle with a polytetrafluoroethylene lining, sealing the reaction kettle, placing the reaction kettle in an environment with the temperature of 150-180 ℃, carrying out heat preservation treatment for 8-10 hours, filtering out solids, washing with water, and drying to obtain nano cobalt diselenide; wherein the mass ratio of the cobalt nitrate to the sodium selenite to the ethylenediamine tetraacetic acid to the deionized water is 1:1.2:6.3: 3.2;
s2, placing the nano cobalt diselenide in a high-temperature furnace at 950 ℃ to sinter for 6 hours to obtain the cobalt diselenide nano powder.
The manufacturing process of the color-changing fiber comprises the following steps:
step 1, preparing a fiber core:
weighing polymethyl methacrylate, cobalt diselenide nano powder and glycidyl methacrylate according to parts by weight respectively, putting the weighed materials into a mixing stirrer at 170 ℃ for melt mixing, and spinning into fibers through a melt spinning process to obtain fiber cores; wherein the parameters of the melt spinning process are as follows: the melting temperature is 230 ℃, the drafting temperature is 110 ℃, and the drafting multiple is 3 times;
step 2, preparing a cladding material:
weighing polyethylene glycol terephthalate, unsaturated polyester resin, polyurethane acrylate and nanocellulose according to parts by weight respectively, and uniformly mixing in a mixing stirrer at 70 ℃ to obtain a cladding material;
step 3, preparing color-changing fibers:
and adding the weighed curing agent into the cladding material, uniformly dispersing, injecting into a fiber coating machine, passing the fiber core through the fiber coating machine to coat the cladding material on the surface layer of the fiber core, and drying at the temperature of 35 ℃ and the humidity of 55% to obtain the color-changing fiber.
Comparative example 2
The color-changing fiber comprises a fiber core and a cladding material wrapped outside the fiber core, wherein the cross-sectional diameter of the fiber core is 35 mu m, and the thickness of the cladding material is 8 mu m;
the fiber core comprises the following components in parts by weight:
95 parts of polymethyl methacrylate and 2.4 parts of glycidyl methacrylate.
The cladding material comprises the following components in parts by weight:
65 parts of polyethylene terephthalate, 30 parts of unsaturated polyester resin, 14 parts of urethane acrylate, 8 parts of nano-cellulose and 10 parts of a curing agent.
Wherein, the unsaturated polyester resin is prepared by the reaction of dihydric alcohol and dibasic acid; the curing agent is obtained by mixing benzoyl peroxide and glutaraldehyde according to the mass ratio of 3: 1.
The manufacturing process of the color-changing fiber comprises the following steps:
step 1, preparing a fiber core:
weighing polymethyl methacrylate and glycidyl methacrylate according to parts by weight respectively, putting the weighed materials into a mixing stirrer at 170 ℃ for melt mixing, and spinning into fibers by a melt spinning process to obtain fiber cores; wherein the parameters of the melt spinning process are as follows: the melting temperature is 230 ℃, the drafting temperature is 110 ℃, and the drafting multiple is 3 times;
step 2, preparing a cladding material:
weighing polyethylene glycol terephthalate, unsaturated polyester resin, polyurethane acrylate and nanocellulose according to parts by weight respectively, and uniformly mixing in a mixing stirrer at 70 ℃ to obtain a cladding material;
step 3, preparing color-changing fibers:
and adding the weighed curing agent into the cladding material, uniformly dispersing, injecting into a fiber coating machine, passing the fiber core through the fiber coating machine to coat the cladding material on the surface layer of the fiber core, and drying at the temperature of 35 ℃ and the humidity of 55% to obtain the color-changing fiber.
In order to more clearly illustrate the invention, the performance of the color-changing fibers prepared in the examples 1 to 3 and the comparative examples 1 to 2 of the invention is detected and compared, wherein the transmittance and the refractive index are detected by using corresponding instruments, the tensile strength and the breaking strength are detected according to the standard GB/T14337-2008, and the light attenuation coefficient is detected by using the standard GB/T15972.40-2008 (the wave band measured by the invention is 850 nm);
the results are shown in Table 1.
TABLE 1 comparison of color-changing fibers of examples and comparative examples
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | |
| Fiber core transmittance (%) | 89 | 90 | 88 | 90 | 92 |
| Refractive index of fiber core | 1.49 | 1.48 | 1.51 | 1.46 | 1.42 |
| Transmittance of clad Material (%) | 92 | 92 | 91 | 92 | 93 |
| Refractive index of cladding material | 1.44 | 1.43 | 1.45 | 1.44 | 1.41 |
| Tensile Strength (MPa) | 125 | 121 | 127 | 112 | 97 |
| Breaking strength (cN/dtex) | 5.4 | 5.1 | 5.5 | 4.3 | 3.7 |
| Optical attenuation coefficient at 850nm (dB/km) | ＜400 | ＜400 | ＜400 | ＞500 | 400～500 |
As can be seen from the above table, the transmittances of the fiber core and the cladding material in examples 1 to 3 of the present invention are 88 to 92, which are reduced compared with comparative examples 1 to 2, but the corresponding refractive index is improved to a certain extent, and the tensile strength and the breaking strength are greatly improved; the reason for the reduction of the optical attenuation coefficient at 850nm is probably that the added scandium disilicate/cobalt diselenide nano powder, polymethyl methacrylate and glycidyl methacrylate are compounded to have more similar refractive index, so that the optical loss is reduced, the optical attenuation coefficient is correspondingly reduced, and the light guide performance is better.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The color-changing fiber is characterized by comprising a fiber core and a cladding material wrapping the fiber core, wherein the fiber core comprises the following components in parts by weight:
80-100 parts of polymethyl methacrylate, 3-6 parts of scandium disilicate/cobalt diselenide nano powder and 1.2-3.6 parts of glycidyl methacrylate.
The cladding material comprises the following components in parts by weight:
50-80 parts of polyethylene terephthalate, 25-35 parts of unsaturated polyester resin, 11-16 parts of polyurethane acrylate, 5-10 parts of nano cellulose and 6-12 parts of curing agent.
2. The color-changing fiber according to claim 1, wherein the unsaturated polyester resin is prepared by reacting any one of dihydric alcohol, trihydric alcohol and tetrahydric alcohol with dibasic acid.
3. The color-changing fiber according to claim 1, wherein the curing agent is obtained by mixing benzoyl peroxide and glutaraldehyde according to a mass ratio of 2-3: 1.
4. The color-changing fiber according to claim 1, wherein the cross-sectional diameter of the fiber core is 20 to 50 μm, and the thickness of the cladding material is 5 to 10 μm.
5. The color-changing fiber of claim 1, wherein the preparation method of the scandium disilicate/cobalt diselenide nano powder comprises the following steps:
s1, weighing cobalt nitrate and sodium selenite, sequentially adding the cobalt nitrate and the sodium selenite into deionized water, stirring until the cobalt nitrate and the sodium selenite are completely dissolved, adding ethylene diamine tetraacetic acid, uniformly mixing, and reacting to obtain nano cobalt diselenide; wherein the mass ratio of the cobalt nitrate to the sodium selenite to the ethylenediamine tetraacetic acid to the deionized water is 1: 1.1-1.3: 5.8-7.2: 2.4-3.6;
s2, weighing scandium oxide, mixing with deionized water, dropwise adding hydrochloric acid, dissolving solids by controlling the reaction temperature, separating out again, continuously stirring for 10-12 h at 20-30 ℃, then carrying out solid-liquid separation on the reaction liquid, washing the separated solids with water, and drying to obtain reaction crystals; wherein the concentration of the hydrochloric acid is 0.1-0.2 mol/L, and the mass ratio of the scandium oxide, the hydrochloric acid and the deionized water is 1: 5-8: 6-12;
s3, weighing ethyl orthosilicate, mixing the ethyl orthosilicate with an ethanol solution with the mass fraction being equal to that of the ethyl orthosilicate, uniformly stirring, adding a reaction crystal, uniformly stirring again, stirring for 4-6 hours at 20-30 ℃, adding nano cobalt diselenide, and continuously stirring for 2-4 hours to obtain a reaction mixture; wherein the mass fraction of the ethanol solution is 20-50%, and the mass ratio of the reaction crystal, the nano cobalt diselenide, the tetraethoxysilane and the ethanol solution is 1: 0.3-0.6: 2.42-2.86: 3-5;
s4, drying the reaction mixture in an oven at 80-100 ℃, crushing into powder, sintering in a high-temperature furnace at 800-1000 ℃ for 5-8 h, and crushing the obtained solid into nano-powder to obtain the scandium disilicate/cobalt diselenide nano-powder.
6. The color-changing fiber according to claim 5, wherein the reaction conditions in S1 are as follows: and (3) uniformly mixing the reaction solution, moving the reaction solution into a reaction kettle with polytetrafluoroethylene as an inner lining, sealing the reaction kettle, placing the reaction kettle in an environment with the temperature of 150-180 ℃, preserving heat for 8-10 hours, filtering out solids, washing with water and drying to obtain the nano cobalt diselenide.
7. The color-changing fiber according to claim 5, wherein the mode of re-precipitating the solid after dissolving in S2 by controlling the reaction temperature is specifically as follows: after the hydrochloric acid is dropwise added, heating to 60-80 ℃, stirring until the hydrochloric acid is completely dissolved, then stopping heating, gradually precipitating solids in the reaction liquid, and continuously stirring until the precipitated solids in the reaction liquid do not increase any more.
8. A process for manufacturing a color-changing fiber according to claim 1, comprising the steps of:
step 1, preparing a fiber core:
weighing polymethyl methacrylate, scandium disilicate/cobalt diselenide nano powder and glycidyl methacrylate according to parts by weight respectively, putting the weighed materials into a mixing stirrer to be melted and mixed uniformly, and preparing fibers to obtain fiber cores;
step 2, preparing a cladding material:
weighing polyethylene glycol terephthalate, unsaturated polyester resin, polyurethane acrylate and nanocellulose according to parts by weight respectively, and placing the materials in a mixing stirrer to be uniformly mixed to obtain a cladding material;
step 3, preparing color-changing fibers:
and adding the weighed curing agent into the cladding material, uniformly dispersing, injecting into a fiber coating machine, passing the fiber core through the fiber coating machine to coat the cladding material on the surface layer of the fiber core, and drying to obtain the color-changing fiber.
9. The process for preparing color-changing fibers according to claim 8, wherein in the step 1, the fibers are prepared by spinning through a melt spinning process; wherein the parameters of the melt spinning process are as follows: the melting temperature is 210-250 ℃, the drafting temperature is 100-120 ℃, and the drafting multiple is 2-5 times.
10. The process for manufacturing the color-changing fiber according to claim 8, wherein in the step 3, the drying temperature is set to be 25-50 ℃ and the humidity is set to be 45-60%.
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