CN110685157B - Method for enhancing ultraviolet resistance of fiber by loading transition metal ions on fiber surface - Google Patents

Method for enhancing ultraviolet resistance of fiber by loading transition metal ions on fiber surface Download PDF

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CN110685157B
CN110685157B CN201911121606.XA CN201911121606A CN110685157B CN 110685157 B CN110685157 B CN 110685157B CN 201911121606 A CN201911121606 A CN 201911121606A CN 110685157 B CN110685157 B CN 110685157B
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fiber
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transition metal
fibers
room temperature
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CN110685157A (en
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胡桢
黄星皓
黄玉东
卢飞
许樨榕
刘鹏翔
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Harbin Institute of Technology
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/368—Hydroxyalkylamines; Derivatives thereof, e.g. Kritchevsky bases
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments

Abstract

The invention discloses a method for enhancing ultraviolet resistance of a fiber by loading transition metal ions on the surface of the fiber, and relates to a method for enhancing the ultraviolet resistance of the fiber. The invention aims to solve the problems that the mechanical property of the fiber is seriously reduced after the existing chemical fiber is subjected to ultraviolet resistance modification, the ultraviolet resistance is not ideal, the operation is complex and the cost is high. The method comprises the following steps: firstly, pretreating the surface of a fiber; secondly, growing a transition metal ion load medium on the surface of the fiber; and thirdly, based on the coordination of transition metal ions of the metal organic framework compound medium, the method for enhancing the ultraviolet resistance of the fiber by loading the transition metal ions on the surface of the fiber is completed.

Description

Method for enhancing ultraviolet resistance of fiber by loading transition metal ions on fiber surface
Technical Field
The present invention relates to a method for enhancing the ultraviolet light resistance of fibers.
Background
Compared with the traditional metal and inorganic ceramic materials, the chemical fiber material has the advantages of high specific strength, high specific stiffness, strong designability, light weight and the like, and is applied to various fields in aeronautics, national defense and life. With the development of science and technology, many special synthetic fibers with excellent properties have appeared, such as polybenzimidazole fibers, aramid fibers, polyparaphenylene benzobisoxazole fibers, and the like. However, chemical bonds in chemical fibers are easily broken after absorbing ultraviolet light, so that the mechanical properties of the fibers are reduced, and the chemical fibers have smooth surfaces and high inertness, so that the application of the chemical fibers in some aspects is limited. At present, fiber ultraviolet light resistance modification methods are mainly divided into a body/in-situ blending strategy and a fiber surface physical modification strategy, wherein the body/in-situ blending strategy mainly comprises a light stabilizer introducing method, an ultraviolet light shielding agent introducing method and a third monomer introducing method; the strategy of physical modification of the fiber surface mainly comprises a coordination method, a sizing treatment method and a chemical grafting method. However, the methods are complex to operate and high in cost, most importantly, the mechanical properties of the modified fibers are damaged to a certain extent, and the ultraviolet light resistance is not ideal, so that the application of the modified fibers is limited.
Disclosure of Invention
The invention provides a method for enhancing the ultraviolet resistance of a fiber by loading transition metal ions on the surface of the fiber, aiming at solving the problems that the mechanical property of the fiber is seriously reduced after the ultraviolet resistance of the existing chemical fiber is modified, the ultraviolet resistance is not ideal, the operation is complex and the cost is high.
A method for enhancing the ultraviolet resistance of a fiber by loading transition metal ions on the surface of the fiber is completed according to the following steps:
firstly, pretreatment of fiber surface:
adding deionized water into dopamine hydrochloride, then carrying out ultrasonic dissolution for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain dopamine hydrochloride solution, extracting fibers for 48-120 h by using acetone to obtain extracted fibers, immersing the extracted fibers into the dopamine hydrochloride solution, adding trihydroxymethyl aminomethane, ultrasonically dissolving for 5 min-60 min by an ultrasonic cleaning machine under the conditions of room temperature and power of 240W-360W to ensure that the pH value of the solution after the trihydroxymethyl aminomethane is added is 8.0-9.0, then in a shaking table with room temperature and frequency of 90 r/min-200 r/min, oscillating for 12-36 h, finally taking out the fiber and repeatedly washing for 1-5 times by deionized water, drying the fiber in an oven at the temperature of 80-120 ℃ for 1-10 h to obtain pretreated fiber;
the concentration of the dopamine hydrochloride solution is 1.5 g/L-2.5 g/L;
secondly, the growth of the transition metal ion loading medium on the surface of the fiber:
adding methanol into metal salt, ultrasonically dissolving for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain a methanol solution of the metal salt, immersing the pretreated fibers into the methanol solution of the metal salt, and oscillating for 5-60 min in a shaking table with the room temperature and the frequency of 90-200 r/min to obtain a metal salt solution containing fibers; adding methanol into an organic ligand, ultrasonically dissolving for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain a methanol solution of the organic ligand, adding the methanol solution of the organic ligand into a metal salt solution containing fibers under the conditions of speed of 0.5-2.0 mL/s, oscillating for 24-72 h in a shaking table with room temperature and frequency of 90-200 r/min, finally taking out the fibers, repeatedly washing the fibers for 1-5 times by using methanol, and drying for 2-10 h in an oven with the temperature of 60-100 ℃ to obtain the fibers loaded with metal organic framework compound media;
the concentration of the methanol solution of the metal salt is 10 g/L-100 g/L; the concentration of the methanol solution of the organic ligand is 10 g/L-100 g/L; the molar ratio of the metal salt to the organic ligand is 1 (2-8);
thirdly, transition metal ion coordination based on the medium of metal organic framework compound:
immersing the fiber loaded with the metal organic framework compound medium in n-hexane to obtain a fiber solution loaded with the metal organic framework compound medium; preparing a transition metal ion solution by using a solvent, dropwise adding the transition metal ion solution into a fiber solution loaded with a metal organic framework compound medium under the condition that the speed is 5-20 mu L/s, oscillating for 4-48 h in a shaking table with the room temperature and the frequency of 90-200 r/min, finally taking out the fiber, and drying for 1-8 h in a drying oven with the temperature of 60-100 ℃, thus completing the method for enhancing the ultraviolet resistance of the fiber by loading the transition metal ion on the surface of the fiber;
the concentration of the transition metal ion solution is 50 mg/mL-1000 mg/mL; the volume ratio of the mass of the fiber loaded with the metal organic framework compound medium to the transition metal ion solution is 1mg (1-10) mL.
The invention has the beneficial effects that: the invention provides the uvioresistant surface modification method which is simple to operate, mild in action condition and small in damage to fibers. The invention pretreats the extracted fiber with dopamine to increase the roughness of the fiber surface, which is convenient for the growth of the metal organic framework compound medium, and then the metal organic framework compound is grown in situ on the fiber surface as the medium for loading transition metal ions, such as Zn (NO)3)2And when the 2-methylimidazole is the metal salt and the organic ligand, the metal framework compound is ZIF-8; co (NO)3)2And when the 2-methylimidazole is the metal salt and the organic ligand, the metal framework compound is ZIF-67; ZrCl4And when terephthalic acid is metal salt and organic ligand, the metal framework compound is UIO-66; ZrCl4And when 2-amino terephthalic acid is used as the metal salt and the organic ligand, the metal framework compound is UIO-66-NH2(ii) a And then, the transition metal ions are combined to the double-bond N atoms in the metal organic framework compound medium in a coordination mode through a double-solvent method of normal hexane and methanol or normal hexane and water, so as to obtain the final modified fiber with the ultraviolet resistance improved. The method for enhancing the ultraviolet resistance of the fiber has low cost and relatively simple operation, and more importantly, compared with the traditional ultraviolet resistance modification method, the method can maintain the mechanical property of the fiber to the maximum extent in the modification process, the mechanical property is equivalent to that of the untreated fiber, and the retention rate of the mechanical property can reach over 84.5 percent when the ultraviolet light irradiates for 144 hours. After the UV irradiation for 144h, the retention rate is still 64.7%. The uvioresistant performance of the fiber is improved, and the fiber can be applied in a plurality of extreme environments, so that the application field of the fiber is greatly widened, and the additional value of the fiber is improved.
Drawings
FIG. 1 is a scanning electron microscope of a fiber loaded with transition metal ions on the surface prepared in the first embodiment;
FIG. 2 is an XPS spectrum of a fiber with transition metal ions loaded on the surface prepared in the first example;
FIG. 3 is a partial peak plot of FIG. 2;
fig. 4 is a graph showing the change of tensile strength after different times of uv irradiation, wherein 1 is a fiber with transition metal ions loaded on the surface prepared in the first example, and 2 is an unmodified fiber.
Detailed Description
The technical solution of the present invention is not limited to the specific embodiments listed below, and includes any combination of the specific embodiments.
The first embodiment is as follows: the method for enhancing the ultraviolet resistance of the fiber by loading the transition metal ions on the surface of the fiber is completed according to the following steps:
firstly, pretreatment of fiber surface:
adding deionized water into dopamine hydrochloride, then carrying out ultrasonic dissolution for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain dopamine hydrochloride solution, extracting fibers for 48-120 h by using acetone to obtain extracted fibers, immersing the extracted fibers into the dopamine hydrochloride solution, adding trihydroxymethyl aminomethane, ultrasonically dissolving for 5 min-60 min by an ultrasonic cleaning machine under the conditions of room temperature and power of 240W-360W to ensure that the pH value of the solution after the trihydroxymethyl aminomethane is added is 8.0-9.0, then in a shaking table with room temperature and frequency of 90 r/min-200 r/min, oscillating for 12-36 h, finally taking out the fiber and repeatedly washing for 1-5 times by deionized water, drying the fiber in an oven at the temperature of 80-120 ℃ for 1-10 h to obtain pretreated fiber;
the concentration of the dopamine hydrochloride solution is 1.5 g/L-2.5 g/L;
secondly, the growth of the transition metal ion loading medium on the surface of the fiber:
adding methanol into metal salt, ultrasonically dissolving for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain a methanol solution of the metal salt, immersing the pretreated fibers into the methanol solution of the metal salt, and oscillating for 5-60 min in a shaking table with the room temperature and the frequency of 90-200 r/min to obtain a metal salt solution containing fibers; adding methanol into an organic ligand, ultrasonically dissolving for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain a methanol solution of the organic ligand, adding the methanol solution of the organic ligand into a metal salt solution containing fibers under the conditions of speed of 0.5-2.0 mL/s, oscillating for 24-72 h in a shaking table with room temperature and frequency of 90-200 r/min, finally taking out the fibers, repeatedly washing the fibers for 1-5 times by using methanol, and drying for 2-10 h in an oven with the temperature of 60-100 ℃ to obtain the fibers loaded with metal organic framework compound media;
the concentration of the methanol solution of the metal salt is 10 g/L-100 g/L; the concentration of the methanol solution of the organic ligand is 10 g/L-100 g/L; the molar ratio of the metal salt to the organic ligand is 1 (2-8);
thirdly, transition metal ion coordination based on the medium of metal organic framework compound:
immersing the fiber loaded with the metal organic framework compound medium in n-hexane to obtain a fiber solution loaded with the metal organic framework compound medium; preparing a transition metal ion solution by using a solvent, dropwise adding the transition metal ion solution into a fiber solution loaded with a metal organic framework compound medium under the condition that the speed is 5-20 mu L/s, oscillating for 4-48 h in a shaking table with the room temperature and the frequency of 90-200 r/min, finally taking out the fiber, and drying for 1-8 h in a drying oven with the temperature of 60-100 ℃, thus completing the method for enhancing the ultraviolet resistance of the fiber by loading the transition metal ion on the surface of the fiber;
the concentration of the transition metal ion solution is 50 mg/mL-1000 mg/mL; the volume ratio of the mass of the fiber loaded with the metal organic framework compound medium to the transition metal ion solution is 1mg (1-10) mL.
The beneficial effects of the embodiment are as follows: the embodiment provides the ultraviolet-resistant surface modification method which is simple to operate, mild in action condition and small in damage to fibers. In the embodiment, the extracted fiber is pretreated by dopamine to increase the surface roughness of the fiber and facilitate the preparation of metal organic framework compoundGrowing medium, and growing metal-organic skeleton compound on the surface of the fiber in situ as medium for supporting transition metal ions, such as Zn (NO)3)2And when the 2-methylimidazole is the metal salt and the organic ligand, the metal framework compound is ZIF-8; co (NO)3)2And when the 2-methylimidazole is the metal salt and the organic ligand, the metal framework compound is ZIF-67; ZrCl4And when terephthalic acid is metal salt and organic ligand, the metal framework compound is UIO-66; ZrCl4And when 2-amino terephthalic acid is used as the metal salt and the organic ligand, the metal framework compound is UIO-66-NH2(ii) a And then, the transition metal ions are combined to the double-bond N atoms in the metal organic framework compound medium in a coordination mode through a double-solvent method of normal hexane and methanol or normal hexane and water, so as to obtain the final modified fiber with the ultraviolet resistance improved. The method for enhancing the ultraviolet resistance of the fiber has the advantages of low cost and relatively simple operation, and more importantly, compared with the traditional ultraviolet resistance modification method, the method can maintain the mechanical property of the fiber to the maximum extent in the modification process, is equivalent to the mechanical property of the untreated fiber, and can keep the mechanical property retention rate to be over 84.5 percent when the fiber is irradiated by ultraviolet light for 144 hours. After the UV irradiation for 144h, the retention rate is still 64.7%. The uvioresistant performance of the fiber is improved, and the fiber can be applied in a plurality of extreme environments, so that the application field of the fiber is greatly widened, and the additional value of the fiber is improved.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the metal salt and the organic ligand in the step two are Zn (NO)3)2And 2-methylimidazole, Co (NO)3)2And 2-methylimidazole, ZrCl4And terephthalic acid or ZrCl4And 2-amino terephthalic acid. The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the fiber in the first step is poly-p-phenylene benzobisoxazole fiber, polybenzimidazole fiber, aramid fiber, carbon fiber, polyester fiber, polyamide fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, polypropylene fiber, polyvinyl chloride fiber or glass fiber. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the solvent in the transition metal ion solution in the third step is methanol or water. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the first to fourth differences of this embodiment from the first to fourth embodiments are: the transition metal ion in the third step is Fe3+Ion, Cu2+Ion, N2+Ions or Cd2+Ions. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: adding deionized water into dopamine hydrochloride in the first step, then ultrasonically dissolving the dopamine hydrochloride for 10-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 300-360W to obtain dopamine hydrochloride solution, extracting the fiber for 48-120 h by using acetone to obtain extracted fiber, immersing the extracted fiber into the dopamine hydrochloride solution, adding tris (hydroxymethyl) aminomethane, ultrasonically dissolving the fiber for 10-60 min by using the ultrasonic cleaning machine under the conditions of room temperature and power of 300-360W to ensure that the pH of the solution after adding tris (hydroxymethyl) aminomethane is 8.0-9.0, then oscillating the solution for 24-36 h in a shaking table with room temperature and frequency of 120-200 r/min, finally taking out the fiber, repeatedly washing the fiber for 1-5 times by using deionized water, drying the fiber for 1-10 h in an oven with the temperature of 100-120 ℃, thus obtaining the pretreated fiber. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: adding methanol into the metal salt, ultrasonically dissolving for 10-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 300-360W to obtain a methanol solution of the metal salt, immersing the pretreated fibers into the methanol solution of the metal salt, and oscillating for 10-60 min in a shaking table with room temperature and frequency of 120-200 r/min to obtain a metal salt solution containing fibers; adding methanol into an organic ligand, ultrasonically dissolving the organic ligand for 10-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 300-360W to obtain a methanol solution of the organic ligand, adding the methanol solution of the organic ligand into a metal salt solution containing fibers under the conditions of speed of 1.0-2.0 mL/s, oscillating the solution for 24-72 h in a shaking table with the room temperature and frequency of 120-200 r/min, finally taking out the fibers, repeatedly washing the fibers for 1-5 times by using methanol, and drying the fibers for 2-10 h in an oven with the temperature of 70-100 ℃ to obtain the fibers loaded with the metal organic framework compound medium. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the concentration of the methanol solution of the metal salt in the step two is 50 g/L-100 g/L; the concentration of the methanol solution of the organic ligand in the step two is 60 g/L-100 g/L; and the molar ratio of the metal salt to the organic ligand in the second step is 1 (4-8). The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: and step three, preparing a transition metal ion solution by using a solvent, dripping the transition metal ion solution into a fiber solution loaded with a metal organic framework compound medium under the condition that the speed is 10-20 mu L/s, oscillating for 12-48 h in a shaking table with the room temperature and the frequency of 120-200 r/min, finally taking out the fiber, and drying for 6-8 h in an oven with the temperature of 70-100 ℃, thus completing the method for enhancing the ultraviolet resistance of the fiber by loading the transition metal ion on the surface of the fiber. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: the concentration of the transition metal ion solution in the third step is 100 mg/mL-1000 mg/mL; the ratio of the mass of the fiber loaded with the metal organic framework compound medium in the third step to the volume of the transition metal ion solution is 1mg (4-10) mL. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a method for enhancing the ultraviolet resistance of a fiber by loading transition metal ions on the surface of the fiber is completed according to the following steps:
firstly, pretreatment of fiber surface:
adding deionized water into dopamine hydrochloride, ultrasonically dissolving the dopamine hydrochloride for 10min by using an ultrasonic cleaning machine under the conditions of room temperature and 300W of power to obtain dopamine hydrochloride solution, extracting fibers for 48h by using acetone to obtain extracted fibers, immersing the extracted fibers into the dopamine hydrochloride solution, adding tris (hydroxymethyl) aminomethane, ultrasonically dissolving the fibers for 10min by using the ultrasonic cleaning machine under the conditions of room temperature and 300W of power to ensure that the pH of the solution is 9.0 after the tris (hydroxymethyl) aminomethane is added, oscillating the solution for 24h in a shaking table with the room temperature and the frequency of 120r/min, finally taking out the fibers, repeatedly washing the fibers for 2 times by using the deionized water, and drying the fibers for 1h in an oven with the temperature of 100 ℃ to obtain pretreated fibers;
the concentration of the dopamine hydrochloride solution is 2 g/L;
secondly, the growth of the transition metal ion loading medium on the surface of the fiber:
adding methanol into metal salt, ultrasonically dissolving for 10min by using an ultrasonic cleaning machine under the conditions of room temperature and 300W of power to obtain a methanol solution of the metal salt, immersing the pretreated fiber in the methanol solution of the metal salt, and oscillating for 10min in a shaking table at room temperature and 120r/min of frequency to obtain a metal salt solution containing fiber; adding methanol into an organic ligand, performing ultrasonic dissolution for 10min by using an ultrasonic cleaning machine under the conditions of room temperature and 300W of power to obtain a methanol solution of the organic ligand, adding the methanol solution of the organic ligand into a metal salt solution containing fibers under the condition of a speed of 1mL/s, oscillating for 24h in a shaking table with the room temperature and a frequency of 120r/min, finally taking out the fibers, repeatedly washing the fibers for 2 times by using the methanol, and drying the fibers for 2h in an oven with the temperature of 70 ℃ to obtain the fibers loaded with the metal-organic framework compound medium;
the concentration of the methanol solution of the metal salt is 59.5 g/L; the concentration of the methanol solution of the organic ligand is 65.7 g/L; the molar ratio of the metal salt to the organic ligand is 1: 4;
thirdly, transition metal ion coordination based on the medium of metal organic framework compound:
immersing the fiber loaded with the metal organic framework compound medium in n-hexane to obtain a fiber solution loaded with the metal organic framework compound medium; using FeCl3·6H2Preparing a transition metal ion solution by using O and a solvent, dropwise adding the transition metal ion solution into a fiber solution loaded with a metal organic framework compound medium under the condition that the speed is 10 mu L/s, oscillating for 12h in a shaking table with the room temperature and the frequency of 120r/min, finally taking out the fiber, and drying for 6h in an oven with the temperature of 70 ℃ to obtain the fiber loaded with the transition metal ions on the surface, namely completing the method for enhancing the ultraviolet resistance of the fiber by using the transition metal ions loaded on the surface of the fiber;
the concentration of the transition metal ion solution is 100 mg/mL; the volume ratio of the mass of the fiber loaded with the metal organic framework compound medium to the transition metal ion solution is 1mg:4 mL.
The metal salt and the organic ligand in the step two are Zn (NO)3)2And 2-methylimidazole.
The fiber in the first step is PBO fiber.
The solvent of the transition metal ion solution in the third step is methanol.
The transition metal ion in the third step is Fe3+Ions.
FIG. 1 is a scanning electron microscope of a fiber loaded with transition metal ions on the surface prepared in the first embodiment. As can be seen from the figure, the fiber surface roughness was significantly increased after the fiber was loaded with the metal-organic framework compound and coordinated with the transition metal ions, and the fiber surface was completely covered with the metal-organic framework compound and the transition metal ions, and the diameter of the modified fiber was increased. The embodiment can well take a metal organic framework compound as a medium on the surface of the fiber, firmly combine transition metal ions in a coordination bond mode, improve the uvioresistant performance of the fiber and further realize the functionalization of the surface of the fiber.
Fig. 2 is an XPS total spectrum of the fiber with transition metal ions loaded on the surface prepared in example one. Fig. 3 is a partial peak plot of fig. 2. As can be seen, C1s, N1s and O1s appeared when the fibers were scanned, because PBO fibers contained C, N and O elements. When iron coordination fibers are involved, the Fe 2p 1/2 and 2p 3/2 peaks, located at 724.6eV and 711.0eV, respectively, appear at binding energies between 700eV and 735eV, demonstrating the successful incorporation of Fe ions as coordination bonds on the surface of the fiber that is surface-loaded with transition metal ions.
Fig. 4 is a graph showing the change of tensile strength after different times of uv irradiation, wherein 1 is a fiber with transition metal ions loaded on the surface prepared in the first example, and 2 is an unmodified fiber. Before 144h, the mechanical property reduction speed of the fiber is relatively slow, the mechanical property retention rate of the unmodified fiber at 144h is 77.2%, and the mechanical property retention rate of the fiber with the surface loaded with transition metal ions prepared in the first embodiment is 84.5%. From 144 hours onward, the mechanical properties of the fibers obviously slide down, the mechanical properties of the unmodified fibers are reduced from original 4.60GPa to 2.33GPa, the property loss is nearly 50%, while the fibers with the transition metal ions loaded on the surfaces prepared in the first embodiment still have 2.89GPa, and the retention rate is 64.7%.

Claims (9)

1. A method for enhancing the ultraviolet resistance of a fiber by loading transition metal ions on the surface of the fiber is characterized by comprising the following steps:
firstly, pretreatment of fiber surface:
adding deionized water into dopamine hydrochloride, then carrying out ultrasonic dissolution for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain dopamine hydrochloride solution, extracting fibers for 48-120 h by using acetone to obtain extracted fibers, immersing the extracted fibers into the dopamine hydrochloride solution, adding trihydroxymethyl aminomethane, ultrasonically dissolving for 5 min-60 min by an ultrasonic cleaning machine under the conditions of room temperature and power of 240W-360W to ensure that the pH value of the solution after the trihydroxymethyl aminomethane is added is 8.0-9.0, then in a shaking table with room temperature and frequency of 90 r/min-200 r/min, oscillating for 12-36 h, finally taking out the fiber and repeatedly washing for 1-5 times by deionized water, drying the fiber in an oven at the temperature of 80-120 ℃ for 1-10 h to obtain pretreated fiber;
the concentration of the dopamine hydrochloride solution is 1.5 g/L-2.5 g/L;
secondly, the growth of the transition metal ion loading medium on the surface of the fiber:
adding methanol into metal salt, ultrasonically dissolving for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain a methanol solution of the metal salt, immersing the pretreated fibers into the methanol solution of the metal salt, and oscillating for 5-60 min in a shaking table with the room temperature and the frequency of 90-200 r/min to obtain a metal salt solution containing fibers; adding methanol into an organic ligand, ultrasonically dissolving for 5-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 240-360W to obtain a methanol solution of the organic ligand, adding the methanol solution of the organic ligand into a metal salt solution containing fibers under the conditions of speed of 0.5-2.0 mL/s, oscillating for 24-72 h in a shaking table with room temperature and frequency of 90-200 r/min, finally taking out the fibers, repeatedly washing the fibers for 1-5 times by using methanol, and drying for 2-10 h in an oven with the temperature of 60-100 ℃ to obtain the fibers loaded with metal organic framework compound media;
the concentration of the methanol solution of the metal salt is 10 g/L-100 g/L; the concentration of the methanol solution of the organic ligand is 10 g/L-100 g/L; the molar ratio of the metal salt to the organic ligand is 1 (2-8);
thirdly, transition metal ion coordination based on the medium of metal organic framework compound:
immersing the fiber loaded with the metal organic framework compound medium in n-hexane to obtain a fiber solution loaded with the metal organic framework compound medium; preparing a transition metal ion solution by using a solvent, dropwise adding the transition metal ion solution into a fiber solution loaded with a metal organic framework compound medium under the condition that the speed is 5-20 mu L/s, oscillating for 4-48 h in a shaking table with the room temperature and the frequency of 90-200 r/min, finally taking out the fiber, and drying for 1-8 h in a drying oven with the temperature of 60-100 ℃, thus completing the method for enhancing the ultraviolet resistance of the fiber by loading the transition metal ion on the surface of the fiber;
the concentration of the transition metal ion solution is 50 mg/mL-1000 mg/mL; the volume ratio of the mass of the fiber loaded with the metal organic framework compound medium to the transition metal ion solution is 1mg (1-10) mL;
the transition metal ion is Fe3+Ions.
2. The method for enhancing the ultraviolet light resistance of the fiber by loading transition metal ions on the surface of the fiber according to claim 1, wherein the method comprises the following steps: the metal salt and the organic ligand in the step two are Zn (NO)3)2And 2-methylimidazole, Co (NO)3)2And 2-methylimidazole, ZrCl4And terephthalic acid or ZrCl4And 2-amino terephthalic acid.
3. The method for enhancing the ultraviolet light resistance of the fiber by loading transition metal ions on the surface of the fiber according to claim 1, wherein the method comprises the following steps: the fiber in the first step is poly-p-phenylene benzobisoxazole fiber, polybenzimidazole fiber, aramid fiber, carbon fiber, polyester fiber, polyamide fiber, polyvinyl alcohol fiber, polyacrylonitrile fiber, polypropylene fiber, polyvinyl chloride fiber or glass fiber.
4. The method for enhancing the ultraviolet light resistance of the fiber by loading transition metal ions on the surface of the fiber according to claim 1, wherein the method comprises the following steps: the solvent in the transition metal ion solution in the third step is methanol or water.
5. The method for enhancing the ultraviolet light resistance of the fiber by loading transition metal ions on the surface of the fiber according to claim 1, wherein the method comprises the following steps: adding deionized water into dopamine hydrochloride in the first step, then ultrasonically dissolving the dopamine hydrochloride for 10-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 300-360W to obtain dopamine hydrochloride solution, extracting the fiber for 48-120 h by using acetone to obtain extracted fiber, immersing the extracted fiber into the dopamine hydrochloride solution, adding tris (hydroxymethyl) aminomethane, ultrasonically dissolving the fiber for 10-60 min by using the ultrasonic cleaning machine under the conditions of room temperature and power of 300-360W to ensure that the pH of the solution after adding tris (hydroxymethyl) aminomethane is 8.0-9.0, then oscillating the solution for 24-36 h in a shaking table with room temperature and frequency of 120-200 r/min, finally taking out the fiber, repeatedly washing the fiber for 1-5 times by using deionized water, drying the fiber for 1-10 h in an oven with the temperature of 100-120 ℃, thus obtaining the pretreated fiber.
6. The method for enhancing the ultraviolet light resistance of the fiber by loading transition metal ions on the surface of the fiber according to claim 1, wherein the method comprises the following steps: adding methanol into the metal salt, ultrasonically dissolving for 10-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 300-360W to obtain a methanol solution of the metal salt, immersing the pretreated fibers into the methanol solution of the metal salt, and oscillating for 10-60 min in a shaking table with room temperature and frequency of 120-200 r/min to obtain a metal salt solution containing fibers; adding methanol into an organic ligand, ultrasonically dissolving the organic ligand for 10-60 min by using an ultrasonic cleaning machine under the conditions of room temperature and power of 300-360W to obtain a methanol solution of the organic ligand, adding the methanol solution of the organic ligand into a metal salt solution containing fibers under the conditions of speed of 1.0-2.0 mL/s, oscillating the solution for 24-72 h in a shaking table with the room temperature and frequency of 120-200 r/min, finally taking out the fibers, repeatedly washing the fibers for 1-5 times by using methanol, and drying the fibers for 2-10 h in an oven with the temperature of 70-100 ℃ to obtain the fibers loaded with the metal organic framework compound medium.
7. The method for enhancing the ultraviolet light resistance of the fiber by loading transition metal ions on the surface of the fiber according to claim 1, wherein the method comprises the following steps: the concentration of the methanol solution of the metal salt in the step two is 50 g/L-100 g/L; the concentration of the methanol solution of the organic ligand in the step two is 60 g/L-100 g/L; and the molar ratio of the metal salt to the organic ligand in the second step is 1 (4-8).
8. The method for enhancing the ultraviolet light resistance of the fiber by loading transition metal ions on the surface of the fiber according to claim 1, wherein the method comprises the following steps: and step three, preparing a transition metal ion solution by using a solvent, dripping the transition metal ion solution into a fiber solution loaded with a metal organic framework compound medium under the condition that the speed is 10-20 mu L/s, oscillating for 12-48 h in a shaking table with the room temperature and the frequency of 120-200 r/min, finally taking out the fiber, and drying for 6-8 h in an oven with the temperature of 70-100 ℃, thus completing the method for enhancing the ultraviolet resistance of the fiber by loading the transition metal ion on the surface of the fiber.
9. The method for enhancing the ultraviolet light resistance of the fiber by loading transition metal ions on the surface of the fiber according to claim 1, wherein the method comprises the following steps: the concentration of the transition metal ion solution in the third step is 100 mg/mL-1000 mg/mL; the ratio of the mass of the fiber loaded with the metal organic framework compound medium in the third step to the volume of the transition metal ion solution is 1mg (4-10) mL.
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