High-toughness glass fiber and preparation method thereof

Abstract

The invention relates to the technical field of glass fibers, and particularly discloses a high-toughness glass fiber and a preparation method thereof, the high-toughness glass fiber comprises a modified glass fiber, a functional solution, a functional monomer and a toughening component; the modified glass fiber is prepared from the following raw materials in parts by weight: 46 to 62 parts of silicon dioxide, 12 to 18 parts of aluminum oxide, 22 to 34 parts of calcium oxide, 3.2 to 4.6 parts of boric oxide, 1.2 to 2.2 parts of zinc oxide and 1.8 to 2.6 parts of zirconium oxide; the functional monomer and the toughening component are added, the functional component is composed of a core-shell structure modified by allyl glycidyl ether, the outer layer of the core-shell structure is a modified silicon dioxide structure obtained by chemically bonding an aminated silicon dioxide structure containing a flexible alkyl long chain and 3, 3 '-dithiodipropionic acid, the inner core is modified nano titanium dioxide, and the core-shell structure is composed of a core-shell structure containing a flexible alkyl long chain and a modified silicon dioxide structure obtained by chemically bonding 3, 3'-dithiodipropionic acid. The toughening component contains an ethylene propylene diene monomer structure, pyridyl, sulfydryl and carboxyl, and the toughness and wear resistance of the glass fiber are improved through the action of each structure.

Description

Technical Field

[0001] The present application relates to the technical field of glass fibers, and more specifically, it relates to a high-toughness glass fiber and a preparation method thereof. Background Art

[0002] Glass fibers have excellent electrical insulation, excellent high-temperature stability, good corrosion resistance, and high mechanical strength. They are often used as reinforcing materials in composite materials and have a wide range of applications in the fields of boat manufacturing, electronics and electrical engineering, and chemical engineering.

[0003] With the continuous increase in the size of composite products, higher requirements are put forward for the various properties of glass fibers. However, glass fibers are relatively brittle and have general toughness. In the prior art, carbon nanotubes are often coated on the fiber surface by electrostatic composite method to utilize the interaction between the surface charges of carbon nanotubes and glass fibers to improve their toughness. However, there is only a weak hydrogen bond between the carbon nanotubes and the glass fibers in the obtained composite fibers, and at the same time, there are problems such as uneven distribution and agglomeration on the surface of the glass fibers, which will lead to an insignificant enhancement effect. In addition, the wear resistance of the existing glass fibers is poor and cannot meet the requirements of special fields such as light military weapons, aviation components, special-purpose automotive components, and wind power generation.

[0004] Therefore, in order to better utilize glass fibers, it is urgent to develop a glass fiber with high toughness and high wear resistance.

[0005] Based on the above statement, the present application provides a high-toughness glass fiber and a preparation method thereof. Summary of the Invention

[0006] In order to solve the problems that glass fibers in the prior art are relatively brittle and have general toughness, and the prior art methods cannot solve the problems such as uneven distribution and easy agglomeration of the reinforcing material on the surface of the glass fibers, and the wear resistance of the glass fibers is poor and cannot meet the requirements in special fields, the present application provides a high-toughness glass fiber and a preparation method thereof.

[0007] A high-toughness glass fiber includes modified glass fibers, a functional solution, a functional monomer, and a toughening component; the modified glass fibers are prepared from the following raw materials in parts by weight: 46-62 parts of silica, 12-18 parts of alumina, 22-34 parts of calcium oxide, 3.2-4.6 parts of boron oxide, 1.2-2.2 parts of zinc oxide, and 1.8-2.6 parts of zirconium oxide;

[0008] The preparation method of the high-toughness glass fiber includes the following steps:

[0009] Step S1, mix the raw materials in the modified glass fibers according to parts by weight, and melt and draw to prepare a glass fiber blank;

[0010] Step S2: Cool and form the glass fiber preform, then wash it with water, and then perform heat treatment to obtain the glass fiber preform.

[0011] Step S3: Place the glass fiber preform in the etching solution, perform ultrasonic oscillation treatment, take it out, then place it in the modification solution, stir and react for 8 - 10 h, wash and dry to obtain the modified glass fiber, where the mass ratio of glass fiber, etching solution, and modification solution is 1:40 - 60:20 - 30.

[0012] Step S4: Immerse the modified glass fiber in the functional solution, then add the functional monomer, toughening component, and benzoin dimethyl ether, stir evenly, irradiate with ultraviolet light for 10 - 20 min, control the irradiation temperature at 55 - 65 °C, then raise the temperature to 85 - 95 °C, stir and react for 0.6 - 1.0 h, filter, and dry to obtain the high - toughness glass fiber, where the mass ratio of modified glass fiber, functional solution, functional monomer, toughening component, and benzoin dimethyl ether is 1.5:12 - 16:0.2 - 0.4:0.4 - 0.6:0.01 - 0.03.

[0013] Preferably, in step S1, the heating temperature of melting is set at 1200 - 1300 °C, keep warm for 4 - 5 h, then raise the temperature to 1400 - 1500 °C at a rate of 10 °C / min, keep warm for 9 - 11 h, and the speed of the wire - drawing machine is set at 2 - 3 m / min.

[0014] Preferably, in step S2, the glass fiber preform is cooled and formed by water cooling, the water - washing temperature is 28 - 32 °C, the heat - treatment temperature is 660 - 720 °C, and the heat - treatment time is 1.4 - 1.8 h.

[0015] Preferably, in S3, the etching solution is composed of ammonium fluoride, 37% hydrochloric acid solution by mass fraction, and deionized water mixed according to the mass ratio of 5:3:250 - 300.

[0016] Preferably, in S4, the functional solution is composed of dopamine hydrochloride and Tris - HCl buffer solution mixed according to the mass ratio of 2 - 10:1000, and the pH value of the Tris - HCl buffer solution is 7.5 - 8.5.

[0017] Preferably, the modification solution is composed of anhydrous DMF, KH - 550, and deionized water mixed according to the mass ratio of 35:0.1 - 0.2:2.

[0018] Preferably, the functional monomer is prepared by the following steps:

[0019] Step A1: Add titanium chloride and deionized water into absolute ethanol, stir evenly, heat up to 35 - 45°C, add dodecyldimethylhydroxypropylsulfobetaine while stirring, then heat up to 112 - 124°C, stir and react for 6 - 8 h. After the reaction is completed, cool to room temperature, centrifuge to precipitate, wash and dry to obtain modified nano-titanium dioxide. Then add it into cyclohexane, stir until homogeneous, adjust the pH value to 8.6 - 9.2, add tetraethyl orthosilicate, heat up to 58 - 64°C, continue to stir for 5 - 8 h. After the reaction is completed, adjust the pH to neutral, centrifuge to precipitate, wash and dry to obtain core-shell particles. Among them, the mass ratio of titanium chloride, deionized water, absolute ethanol and dodecyldimethylhydroxypropylsulfobetaine is 3 - 4:26 - 40:56 - 64:0.12 - 0.16, and the mass ratio of modified nano-titanium dioxide, cyclohexane and tetraethyl orthosilicate is 2.2 - 2.8:60 - 80:0.46 - 0.52. During the above reaction process, first prepare modified nano-titanium dioxide by the LSS method, and then use tetraethyl orthosilicate as the silicon source to coat it to obtain core-shell particles;

[0020] Step A2: Ultrasonically mix the core-shell particles, deionized water, absolute ethanol and KH-550 evenly, heat up to 48 - 56°C, continue to stir for 5.2 - 5.8 h, centrifuge, wash and dry to obtain amino-functionalized core-shell particles. Add the amino-functionalized core-shell particles into anhydrous DMF, stir evenly, dropwise add a mixture a of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF. After dropping, heat up to 78 - 82°C, stir and react for 2.4 - 2.8 h. After the reaction is completed, centrifuge to precipitate, wash and dry to obtain dithiol monomers. Among them, the mass ratio of core-shell particles, deionized water, absolute ethanol and KH-550 is 2.4 - 3.2:11 - 13:22 - 30:0.16 - 0.30, and the mass ratio of amino-functionalized core-shell particles, anhydrous DMF and mixture a is 2.2:40 - 50:16. In mixture a, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF is 0.40 - 0.48:0.20 - 0.24:0.36 - 0.44:10. First, treat the core-shell particles with KH-550 to obtain amino-functionalized core-shell particles. The carboxyl group of 3,3'-dithiobispropionic acid can undergo an amidation reaction with the amino group on the surface of the amino-functionalized core-shell particles and graft onto the surface of the core-shell particles, reducing the agglomeration of the core-shell particles, improving the dispersion performance of the core-shell particles, and enhancing the compatibility of the core-shell particles. At the same time, the remaining carboxyl groups on the dithiol monomers can also participate in the subsequent reaction process;

[0021] Step A3: Add the dithiol monomer into anhydrous DMF, heat up to 45 - 55 °C, stir evenly, adjust the pH to 9 - 10, while stirring, dropwise add the mixed solution b of allyl glycidyl ether and isopropanol, control to finish dropping within 30 min. After dropping, heat up to 76 - 82 °C, continue stirring and reacting for 8 - 12 h, adjust the pH to neutral, rotary evaporate, wash and dry to obtain the functional monomer. Among them, the mass ratio of the dithiol monomer, anhydrous DMF and the mixed solution b is 2 - 4:36 - 42:15 - 25. In the mixed solution b, the mass ratio of allyl glycidyl ether and isopropanol is 1.2 - 1.6:12 - 22. During the above reaction process, using anhydrous DMF as the solvent, the carboxyl group on the dithiol monomer undergoes a ring-opening esterification reaction with the epoxy group on allyl glycidyl ether to obtain the functional monomer.

[0022] Preferably, the toughening component is prepared by the following steps:

[0023] Step B1: Add ethylene propylene diene monomer rubber into n-hexane, stir to dissolve, heat up to 45 - 55 °C, then add formic acid and Tween - 80, stir evenly, dropwise add hydrogen peroxide, control to finish dropping within 30 min. After dropping, stir and react for 8 - 10 h. After the reaction ends, add the sodium carbonate aqueous solution, continue stirring for 10 - 12 min, stand for 15 - 25 min, wash, then add it into anhydrous ethanol, flocculate and precipitate for 2 - 3 h, dry to obtain the epoxidized ethylene propylene diene monomer rubber. Among them, the mass ratio of ethylene propylene diene monomer rubber, n-hexane, formic acid, Tween - 80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 30:450 - 550:0.5 - 0.6:1.5 - 2.5:6 - 8:15 - 25:110 - 120, and the mass fraction of the sodium carbonate aqueous solution is 0.04 - 0.08%;

[0024] Step B2: Add the epoxy group-containing ethylene propylene diene monomer rubber into toluene, stir evenly, heat up to 65 - 75 °C, while stirring, dropwise add the mixed solution c of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF, control to finish dropping within 15 min. After dropping, continue stirring and reacting for 6 - 8 h, centrifuge, wash the precipitate, dry to obtain the toughening component. Among them, the mass ratio of the epoxy group-containing ethylene propylene diene monomer rubber, toluene and the mixed solution c is 18 - 22:240 - 260:52 - 64. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF is 0.5 - 0.8:8 - 10:45 - 55. During the above reaction process, using toluene as the solvent and tetrabutylammonium bromide as the catalyst, 4-mercaptopyridine dicarboxylic acid undergoes a ring-opening esterification reaction with the epoxy group-containing ethylene propylene diene monomer rubber to obtain the toughening component.

[0025] In summary, the present application has the following beneficial effects:

[0026] In order to improve the toughness and wear resistance of glass fibers, this application starts from two aspects. One is to add a toughening component. The toughening component contains an ethylene-propylene-diene monomer (EPDM) structure, a pyridyl group, a mercapto group, and a carboxyl group. The presence of the EPDM structure has good wear resistance on the one hand. The grafted epoxy group on it can not only form a chemical bond with the amino group on polydopamine in the functional solution to further improve the toughness of the glass fiber, but also, as a strongly polar side group, enhance the compatibility between the EPDM structure and the glass fiber, further improving the toughness of the glass fiber. The presence of the pyridyl group not only has a rigid structure with good wear resistance, but also can form a hydrogen bond with the hydroxyl group on polydopamine in the functional solution, further improving the toughness of the glass fiber. The presence of the mercapto group can form a chemical bond with the unsaturated double bond on the functional monomer, further improving the toughness of the glass fiber. The presence of the carboxyl group can serve as an anchoring point to undergo a ring-opening reaction with the epoxy group of the functional monomer, further increasing the crosslinking degree and improving the toughness of the glass fiber. The other is to add a functional monomer, which is composed of a core-shell structure modified by allyl glycidyl ether. The outer layer of the core-shell structure is a modified silica structure obtained by chemically bonding an amino-functionalized silica structure containing a flexible alkyl long chain and 3,3'-dithiodipropionic acid, and the inner core is modified nano-titanium dioxide. The presence of the modified silica structure has good wear resistance on the one hand and can improve the wear resistance of the glass fiber together with nano-titanium dioxide. On the other hand, the grafted dynamic disulfide bond on it can improve the self-healing performance of the functional monomer, further improving the wear resistance and toughness of the glass fiber. Introducing it into the glass fiber can play a synergistic role with the toughening component to jointly improve the toughness and wear resistance of the glass fiber. Detailed Embodiments

[0027] To make the embodiments of this application easier to understand, the following will detail this application with specific examples. These examples are only illustrative and are not limited to the application scope of this application.

[0028] Preparation Examples 1-3 and Comparative Preparation Examples 1-2 provide a functional monomer.

[0029] Preparation Example 1

[0030] This preparation example provides a functional monomer, which is prepared by the following steps:

[0031] Step A1: Add titanium chloride and deionized water into absolute ethanol, stir for 16 min at a rotation speed of 500 rpm until uniform, heat up to 35 °C, add dodecyldimethylhydroxypropylsulfobetaine while stirring, then heat up to 112 °C, maintain the rotation speed unchanged, and continue stirring and reacting for 6 h. After the reaction is completed, cool to room temperature, centrifuge to precipitate, and then wash 3 times with absolute ethanol and deionized water successively, and dry at 55 °C to constant weight to obtain modified nano-titanium dioxide. Then add it into cyclohexane, stir for 25 min at a rotation speed of 500 rpm until uniform, adjust the pH value to 8.6 with 0.4 M sodium hydroxide aqueous solution, then add tetraethyl orthosilicate, heat up to 58 °C, and continue stirring for 5 h. After the reaction is completed, adjust the pH to neutral with 0.3 M hydrochloric acid aqueous solution, centrifuge to precipitate, and then wash 3 times with absolute ethanol and deionized water successively, and dry at 60 °C to constant weight to obtain core-shell particles. Among them, the mass ratio of titanium chloride, deionized water, absolute ethanol and dodecyldimethylhydroxypropylsulfobetaine is 3:26:56:0.12, and the mass ratio of modified nano-titanium dioxide, cyclohexane and tetraethyl orthosilicate is 2.2:60:0.46;

[0032] Step A2: Add core-shell particles, deionized water, absolute ethanol and KH-550, and ultrasonicate for 40 min at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 w until uniform, heat up to 48 °C, and continue stirring for 5.2 h, then centrifuge, and then wash 3 times with absolute ethanol and deionized water successively, and dry at 50 °C to constant weight to obtain amino-functionalized core-shell particles. Add the amino-functionalized core-shell particles into anhydrous DMF, control the rotation speed at 550 rpm and stir for 15 min until uniform, dropwise add the mixed solution a of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF. After dropping, heat up to 78 °C and stir and react for 2.4 h. After the reaction is completed, centrifuge, and then wash 3 times with absolute ethanol and deionized water successively, and dry at 65 °C to constant weight to obtain dithiol monomers. Among them, the mass ratio of core-shell particles, deionized water, absolute ethanol and KH-550 is 2.4:11:22:0.16, and the mass ratio of amino-functionalized core-shell particles, anhydrous DMF and mixed solution a is 2.2:40:16. In the mixed solution a, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF is 0.4:0.2:0.36:10;

[0033] Step A3: Add the disulfide monomer into anhydrous DMF, heat up to 45°C, stir at a rotation speed of 600 rpm for 16 min until uniform, adjust the pH to 9 with 0.6 M aqueous sodium hydroxide solution, dropwise add the mixed solution b of allyl glycidyl ether and isopropanol while stirring, control to finish dropping within 30 min. After dropping, heat up to 76°C, keep the rotation speed unchanged, continue stirring and reacting for 8 h, then adjust the pH to neutral with 0.8 M aqueous hydrochloric acid solution, control the rotary evaporation temperature at 82°C, rotary evaporate to remove anhydrous DMF, then wash with anhydrous ethanol and deionized water 3 times in sequence, and dry at 55°C to constant weight to obtain the functional monomer. Among them, the mass ratio of the disulfide monomer, anhydrous DMF and the mixed solution b is 2:36:15, and in the mixed solution b, the mass ratio of allyl glycidyl ether and isopropanol is 1.2:12.

[0034] Preparation Example 2

[0035] This preparation example provides a functional monomer, which is prepared by the following steps:

[0036] Step A1: Add titanium chloride and deionized water into anhydrous ethanol, stir at a rotation speed of 600 rpm for 20 min until uniform, heat up to 40°C, add dodecyldimethylhydroxypropylsulfobetaine while stirring, then heat up to 118°C, keep the rotation speed unchanged, continue stirring and reacting for 7 h. After the reaction ends, cool to room temperature, centrifuge to precipitate, then wash with anhydrous ethanol and deionized water 4 times in sequence, and dry at 60°C to constant weight to obtain modified nano-titanium dioxide. Then add it into cyclohexane, stir at a rotation speed of 550 rpm for 30 min until uniform, adjust the pH value to 8.9 with 0.6 M aqueous sodium hydroxide solution, then add tetraethyl orthosilicate, heat up to 61°C, continue stirring for 6.5 h. After the reaction ends, adjust the pH to neutral with 0.4 M aqueous hydrochloric acid solution, centrifuge to precipitate, then wash with anhydrous ethanol and deionized water 4 times in sequence, and dry at 65°C to constant weight to obtain core-shell particles. Among them, the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyldimethylhydroxypropylsulfobetaine is 3.5:28:58:0.14, and the mass ratio of modified nano-titanium dioxide, cyclohexane and tetraethyl orthosilicate is 2.5:70:0.49;

[0037] Step A2: Add the core-shell particles, deionized water, absolute ethanol, and KH-550, and ultrasonicate for 45 min until homogeneous at an ultrasonic frequency of 30 kHz and an ultrasonic power of 450 W. Then raise the temperature to 52 °C and continue stirring for 5.5 h. Centrifuge, and then wash successively with absolute ethanol and deionized water 4 times each. Dry at 54 °C to constant weight to obtain amino-functionalized core-shell particles. Add the amino-functionalized core-shell particles to anhydrous DMF, and stir at a rotation speed of 600 rpm for 20 min until homogeneous. Dropwise add the mixed solution a of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid, and anhydrous DMF. After dropping, raise the temperature to 105 °C and stir and react for 2.6 h. After the reaction is completed, centrifuge, and then wash successively with absolute ethanol and deionized water 4 times each. Dry at 70 °C to constant weight to obtain the dithiol monomer. Among them, the mass ratio of the core-shell particles, deionized water, absolute ethanol, and KH-550 is 2.8:12:26:0.23, the mass ratio of the amino-functionalized core-shell particles, anhydrous DMF, and the mixed solution a is 2.2:45:16. In the mixed solution a, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid, and anhydrous DMF is 0.44:0.22:0.40:10;

[0038] Step A3: Add the dithiol monomer to anhydrous DMF, raise the temperature to 50 °C, and stir at a rotation speed of 650 rpm for 18 min until homogeneous. Adjust the pH to 9.5 with 0.8 M aqueous sodium hydroxide solution, and dropwise add the mixed solution b of allyl glycidyl ether and isopropyl alcohol while stirring, controlling to finish dropping within 30 min. After dropping, raise the temperature to 79 °C, keep the rotation speed unchanged, and continue stirring and reacting for 10 h. Then adjust the pH to neutral with 1.0 M aqueous hydrochloric acid solution, control the rotary evaporation temperature to 84 °C, rotary evaporate to remove anhydrous DMF, and then wash successively with absolute ethanol and deionized water 4 times each. Dry at 60 °C to constant weight to obtain the functional monomer. Among them, the mass ratio of the dithiol monomer, anhydrous DMF, and the mixed solution b is 3:39:20. In the mixed solution b, the mass ratio of allyl glycidyl ether and isopropyl alcohol is 1.4:18.

[0039] Preparation Example 3

[0040] This preparation example provides a functional monomer, which is prepared by the following steps:

[0041] Step A1: Add titanium chloride and deionized water into absolute ethanol, stir at a speed of 700 rpm for 24 min until uniform, heat up to 45 °C, add dodecyldimethylhydroxypropylsulfobetaine while stirring, then heat up to 124 °C, stir and react for 8 h. After the reaction is completed, cool to room temperature, centrifuge to precipitate, and then wash 5 times with absolute ethanol and deionized water successively, dry at 65 °C until constant weight to obtain modified nano-titanium dioxide. Then add it into cyclohexane, stir at a speed of 600 rpm for 35 min until uniform, adjust the pH value to 9.2 with 0.8 M sodium hydroxide aqueous solution, add tetraethyl orthosilicate, heat up to 64 °C, continue to stir for 8 h. After the reaction is completed, adjust the pH to neutral with 0.5 M hydrochloric acid aqueous solution, centrifuge to precipitate, and then wash 5 times with absolute ethanol and deionized water successively, dry at 70 °C until constant weight to obtain core-shell particles. Among them, the mass ratio of titanium chloride, deionized water, absolute ethanol and dodecyldimethylhydroxypropylsulfobetaine is 4:40:64:0.16, and the mass ratio of modified nano-titanium dioxide, cyclohexane and tetraethyl orthosilicate is 2.8:80:0.52;

[0042] Step A2: Add core-shell particles, deionized water, absolute ethanol and KH-550, and ultrasonicate at an ultrasonic frequency of 40 kHz and an ultrasonic power of 550 w for 35 min until uniform, heat up to 56 °C, continue to stir for 5.8 h, then wash 5 times with absolute ethanol and deionized water successively, dry at 65 °C until constant weight to obtain amino-functionalized core-shell particles. Add the amino-functionalized core-shell particles into anhydrous DMF, stir at a speed of 650 rpm for 25 min until uniform, dropwise add a mixed solution a of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF. After dropping, heat up to 116 °C, stir and react for 2.8 h. After the reaction is completed, centrifuge, and then wash 5 times with absolute ethanol and deionized water successively, dry at 75 °C until constant weight to obtain dithiol monomers. Among them, the mass ratio of core-shell particles, deionized water, absolute ethanol and KH-550 is 3.2:13:30:0.30, and the mass ratio of amino-functionalized core-shell particles, anhydrous DMF and mixed solution a is 2.2:50:16. In the mixed solution a, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF is 0.48:0.24:0.44:10;

[0043] Step A3: Add the disulfide monomer into anhydrous DMF, heat up to 55 °C, stir at a rotation speed of 700 rpm for 20 min until homogeneous, adjust the pH to 10 with 1.0 M aqueous sodium hydroxide solution, dropwise add the mixed solution b of allyl glycidyl ether and isopropanol while stirring, control to finish dropping within 30 min. After dropping, heat up to 82 °C, keep the rotation speed unchanged, continue to stir and react for 12 h, then adjust the pH to neutral with 1.2 M aqueous hydrochloric acid solution, control the rotary evaporation temperature at 86 °C, rotary evaporate to remove anhydrous DMF, then wash with anhydrous ethanol and deionized water 5 times in sequence, dry at 65 °C to constant weight to obtain the functional monomer. Among them, the mass ratio of the disulfide monomer, anhydrous DMF and the mixed solution b is 4:42:25, and in the mixed solution b, the mass ratio of allyl glycidyl ether and isopropanol is 1.6:22.

[0044] Comparative Preparation Example 1

[0045] This comparative preparation example provides a functional monomer, which is prepared by the following steps:

[0046] Step A1: Add titanium chloride and deionized water into anhydrous ethanol, stir at a rotation speed of 500 rpm for 16 min until homogeneous, heat up to 35 °C, add dodecyldimethylhydroxypropylsulfobetaine while stirring, then heat up to 112 °C, keep the rotation speed unchanged, continue to stir and react for 6 h. After the reaction ends, cool to room temperature, centrifuge and precipitate, then wash with anhydrous ethanol and deionized water 3 times in sequence, dry at 55 °C to constant weight to obtain modified nano-titanium dioxide. Then add it into cyclohexane, stir at a rotation speed of 500 rpm for 25 min until homogeneous, adjust the pH value to 8.6 with 0.4 M aqueous sodium hydroxide solution, then add tetraethyl orthosilicate, heat up to 58 °C, continue to stir for 5 h. After the reaction ends, adjust the pH to neutral with 0.3 M aqueous hydrochloric acid solution, centrifuge and precipitate, then wash with anhydrous ethanol and deionized water 3 times in sequence, dry at 60 °C to constant weight to obtain the core-shell particles. Among them, the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyldimethylhydroxypropylsulfobetaine is 3:26:56:0.12, and the mass ratio of modified nano-titanium dioxide, cyclohexane and tetraethyl orthosilicate is 2.2:60:0.46;

[0047] Step A2: The core-shell particles, deionized water, absolute ethanol, and KH-550 were ultrasonically treated at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 W for 40 min until homogeneous. Then the temperature was raised to 48 °C, and stirring was continued for 5.2 h. After centrifugation, the product was washed successively with absolute ethanol and deionized water three times each, and then dried at 50 °C to a constant weight to obtain amino-functionalized core-shell particles. The amino-functionalized core-shell particles were added to anhydrous DMF, and stirred at a rotation speed of 550 rpm for 15 min until homogeneous. A mixed solution a of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-thiodipropionic acid, and anhydrous DMF was added dropwise. After the addition was complete, the temperature was raised to 78 °C, and the reaction was stirred for 2.4 h. After the reaction ended, centrifugation was performed, and the product was washed successively with absolute ethanol and deionized water three times each, and then dried at 65 °C to a constant weight to obtain the disulfide monomer. Among them, the mass ratio of the core-shell particles, deionized water, absolute ethanol, and KH-550 was 2.4:11:22:0.16, the mass ratio of the amino-functionalized core-shell particles, anhydrous DMF, and the mixed solution a was 2.2:40:16. In the mixed solution a, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-thiodipropionic acid, and anhydrous DMF was 0.4:0.2:0.36:10;

[0048] Step A3: The disulfide monomer was added to anhydrous DMF, and the temperature was raised to 45 °C. It was stirred at a rotation speed of 600 rpm for 16 min until homogeneous. The pH was adjusted to 9 with a 0.6 M aqueous sodium hydroxide solution. A mixed solution b of allyl glycidyl ether and isopropanol was added dropwise while stirring, and the addition was controlled to be completed within 30 min. After the addition was complete, the temperature was raised to 76 °C, and the rotation speed was maintained unchanged while stirring the reaction for 8 h. Then the pH was adjusted to neutral with a 0.8 M aqueous hydrochloric acid solution. The rotary evaporation temperature was controlled at 82 °C, and anhydrous DMF was removed by rotary evaporation. Then the product was washed successively with absolute ethanol and deionized water three times each, and then dried at 55 °C to a constant weight to obtain the functional monomer. Among them, the mass ratio of the disulfide monomer, anhydrous DMF, and the mixed solution b was 2:36:15. In the mixed solution b, the mass ratio of allyl glycidyl ether and isopropanol was 1.2:12.

[0049] Comparative Preparation Example 2

[0050] This comparative preparation example provides a functional monomer, which is prepared by the following steps:

[0051] Step A1: Add titanium chloride and deionized water into absolute ethanol, stir for 16 min at a rotation speed of 500 rpm until homogeneous, heat up to 35 °C, add dodecyldimethylhydroxypropyl sulfobetaine while stirring, then heat up to 112 °C, maintain the rotation speed unchanged, and continue stirring and reacting for 6 h. After the reaction is completed, cool to room temperature, centrifuge to precipitate, and then wash 3 times with absolute ethanol and deionized water in sequence, dry at 55 °C to constant weight to obtain modified nano-titanium dioxide. Then add it into cyclohexane, stir for 25 min at a rotation speed of 500 rpm until homogeneous, adjust the pH value to 8.6 with 0.4 M sodium hydroxide aqueous solution, then add tetraethyl orthosilicate, heat up to 58 °C, and continue stirring for 5 h. After the reaction is completed, adjust the pH to neutral with 0.3 M hydrochloric acid aqueous solution, centrifuge to precipitate, and then wash 3 times with absolute ethanol and deionized water in sequence, dry at 60 °C to constant weight to obtain core-shell particles. Among them, the mass ratio of titanium chloride, deionized water, absolute ethanol and dodecyldimethylhydroxypropyl sulfobetaine is 3:26:56:0.12, and the mass ratio of modified nano-titanium dioxide, cyclohexane and tetraethyl orthosilicate is 2.2:60:0.46;

[0052] Step A2: Add core-shell particles, deionized water, absolute ethanol and KH-550, and ultrasonicate for 40 min at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 w until homogeneous, heat up to 48 °C, and continue stirring for 5.2 h. Centrifuge, and then wash 3 times with absolute ethanol and deionized water in sequence, dry at 50 °C to constant weight to obtain amino-functionalized core-shell particles. Add the amino-functionalized core-shell particles into anhydrous DMF, stir at a rotation speed of 550 rpm for 15 min until homogeneous, dropwise add a mixture a of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF. After dropping, heat up to 78 °C and stir and react for 2.4 h. After the reaction is completed, centrifuge, and then wash 3 times with absolute ethanol and deionized water in sequence, dry at 65 °C to constant weight to obtain dithiol monomers. Among them, the mass ratio of core-shell particles, deionized water, absolute ethanol and KH-550 is 2.4:11:22:0.16, and the mass ratio of amino-functionalized core-shell particles, anhydrous DMF and mixture a is 2.2:40:16. In mixture a, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF is 0.4:0.2:0.36:10;

[0053] Step A3: Add the dithiol monomer into anhydrous DMF, heat up to 45 °C, stir for 16 min at a rotation speed of 600 rpm until homogeneous, adjust the pH to 9 with 0.6 M aqueous sodium hydroxide solution, dropwise add the mixed solution b of isopropyl glycidyl ether and isopropanol while stirring, control to finish dropping within 30 min. After dropping, heat up to 76 °C, keep the rotation speed unchanged, continue to stir and react for 8 h, then adjust the pH to neutral with 0.8 M aqueous hydrochloric acid solution, control the rotary evaporation temperature at 82 °C, rotary evaporate to remove anhydrous DMF, then wash with anhydrous ethanol and deionized water three times in sequence, and dry at 55 °C to constant weight to obtain the functional monomer. Among them, the mass ratio of the dithiol monomer, anhydrous DMF and the mixed solution b is 2:36:15, and in the mixed solution b, the mass ratio of isopropyl glycidyl ether and isopropanol is 1.2:12.

[0054] Preparation Examples 4 - 6 and Comparative Preparation Examples 3 - 5 provide a toughening component.

[0055] Preparation Example 4

[0056] This preparation example provides a toughening component, which is prepared by the following steps:

[0057] Step B1: Add ethylene propylene diene monomer rubber into n - hexane, stir to dissolve, heat up to 45 °C, then add formic acid and Tween - 80, stir at a rotation speed of 500 rpm for 16 min until homogeneous, dropwise add hydrogen peroxide while stirring, control to finish dropping within 30 min. After dropping, stir and react for 8 h. After the reaction ends, add an aqueous sodium carbonate solution with a mass fraction of 0.04%, continue to stir for 10 min, stand for 15 min, wash with deionized water three times, then add into anhydrous ethanol, flocculate and precipitate for 2 h, and dry at 50 °C to constant weight to obtain epoxidized ethylene propylene diene monomer rubber. Among them, the mass ratio of ethylene propylene diene monomer rubber, n - hexane, formic acid, Tween - 80, hydrogen peroxide, aqueous sodium carbonate solution and anhydrous ethanol is 30:450:0.5:1.5:6:15:110;

[0058] Step B2: Add the epoxy - functionalized ethylene propylene diene monomer rubber into toluene, stir at a rotation speed of 550 rpm for 20 min until homogeneous, heat up to 65 °C, dropwise add the mixed solution c of tetrabutylammonium bromide, 4 - mercaptopyridine - 2,6 - dicarboxylic acid and anhydrous DMF while stirring, control to finish dropping within 15 min. After dropping, continue to stir and react for 6 h, centrifuge, wash the precipitate with anhydrous ethanol and deionized water three times, and dry at 55 °C to constant weight to obtain the toughening component. Among them, the mass ratio of the epoxy - functionalized ethylene propylene diene monomer rubber, toluene and the mixed solution c is 18:240:52, and in the mixed solution c, the mass ratio of tetrabutylammonium bromide, 4 - mercaptopyridine - 2,6 - dicarboxylic acid and anhydrous DMF is 0.5:8:45.

[0059] Preparation Example 5

[0060] This preparation example provides a toughening component, which is prepared by the following steps:

[0061] Step B1: Add ethylene propylene diene monomer (EPDM) rubber into n-hexane, stir to dissolve, heat up to 50 °C, then add formic acid and Tween-80, stir at a controlled speed of 550 rpm for 20 min until uniform, dropwise add hydrogen peroxide, control to finish dropping within 30 min. After dropping, stir and react for 9 h. After the reaction ends, add an aqueous sodium carbonate solution with a mass fraction of 0.06%, continue to stir for 11 min, let stand for 20 min, wash with deionized water 4 times, then add to anhydrous ethanol, carry out flocculation precipitation for 2.5 h, and dry at 55 °C to constant weight to obtain epoxidized EPDM rubber. Among them, the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, aqueous sodium carbonate solution and anhydrous ethanol is 30:500:0.55:2.0:7:20:115;

[0062] Step B2: Add epoxidized EPDM rubber into toluene, stir at a controlled speed of 600 rpm for 25 min until uniform, heat up to 70 °C, while stirring, dropwise add a mixed solution c of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF, control to finish dropping within 15 min. After dropping, continue to stir and react for 7 h, centrifuge, wash the precipitate with anhydrous ethanol and deionized water 4 times, and dry at 60 °C to constant weight to obtain the toughening component. Among them, the mass ratio of epoxidized EPDM rubber, toluene and mixed solution c is 20:250:58. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF is 0.65:9:50.

[0063] Preparation Example 6

[0064] This preparation example provides a toughening component, which is prepared by the following steps:

[0065] Step B1: Add EPDM rubber into n-hexane, stir to dissolve, heat up to 55 °C, then add formic acid and Tween-80, stir at a controlled speed of 600 rpm for 25 min until uniform, dropwise add hydrogen peroxide, control to finish dropping within 30 min. After dropping, stir and react for 10 h. After the reaction ends, add an aqueous sodium carbonate solution with a mass fraction of 0.08%, continue to stir for 12 min, let stand for 25 min, wash with deionized water 5 times, then add to anhydrous ethanol, carry out flocculation precipitation for 3 h, and dry at 60 °C to constant weight to obtain epoxidized EPDM rubber. Among them, the mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, aqueous sodium carbonate solution and anhydrous ethanol is 30:550:0.6:2.5:8:25:120;

[0066] Step B2: Add the epoxy group-containing ethylene propylene diene monomer rubber into toluene, stir at a rotation speed of 650 rpm for 30 min until uniform, heat up to 75 °C, and dropwise add the mixed solution c of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF while stirring, controlling to finish dropping within 15 min. After dropping, continue to stir and react for 8 h, centrifuge, wash the precipitate 5 times with absolute ethanol and deionized water, and dry at 70 °C to constant weight to obtain the toughening component. Among them, the mass ratio of the epoxy group-containing ethylene propylene diene monomer rubber, toluene and the mixed solution c is 22:260:64, and in the mixed solution c, the mass ratio of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF is 0.8:10:55.

[0067] Comparative Preparation Example 3

[0068] This comparative preparation example provides a toughening component, which is prepared by the following steps:

[0069] Step B1: Add ethylene propylene diene monomer rubber into n-hexane, stir to dissolve, heat up to 45 °C, then add formic acid and Tween-80, stir at a rotation speed of 500 rpm for 16 min until uniform, dropwise add hydrogen peroxide while stirring, controlling to finish dropping within 30 min. After dropping, stir and react for 8 h. After the reaction ends, add an aqueous solution of sodium carbonate with a mass fraction of 0.04%, continue to stir for 10 min, stand for 15 min, wash 3 times with deionized water, then add to absolute ethanol, and flocculate the precipitate for 2 h, and dry at 50 °C to constant weight to obtain epoxidized ethylene propylene diene monomer rubber. Among them, the mass ratio of ethylene propylene diene monomer rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, aqueous solution of sodium carbonate and absolute ethanol is 30:450:0.5:1.5:6:15:110;

[0070] Step B2: Add the epoxy group-containing ethylene propylene diene monomer rubber into toluene, stir at a rotation speed of 550 rpm for 20 min until uniform, heat up to 65 °C, and dropwise add the mixed solution c of tetrabutylammonium bromide, 4-mercaptobenzoic acid and anhydrous DMF while stirring, controlling to finish dropping within 15 min. After dropping, continue to stir and react for 6 h, centrifuge, wash the precipitate 3 times with absolute ethanol and deionized water, and dry at 55 °C to constant weight to obtain the toughening component. Among them, the mass ratio of the epoxy group-containing ethylene propylene diene monomer rubber, toluene and the mixed solution c is 18:240:52, and in the mixed solution c, the mass ratio of tetrabutylammonium bromide, 4-mercaptobenzoic acid and anhydrous DMF is 0.5:8:45.

[0071] Comparative Preparation Example 4

[0072] This comparative preparation example provides a toughening component, which is prepared by the following steps:

[0073] Step B1: Add ethylene propylene diene monomer rubber (EPDM) into n - hexane, stir to dissolve, heat up to 45 °C, then add formic acid and Tween - 80, stir at a speed of 500 rpm for 16 min until uniform. While stirring, dropwise add hydrogen peroxide, and control to finish dropping within 30 min. After dropping, stir and react for 8 h. After the reaction ends, add an aqueous sodium carbonate solution with a mass fraction of 0.04%, continue to stir for 10 min, let it stand for 15 min, wash with deionized water 3 times, then add it into absolute ethanol, flocculate and precipitate for 2 h, and dry at 50 °C to constant weight to obtain epoxidized ethylene propylene diene monomer rubber. Among them, the mass ratio of ethylene propylene diene monomer rubber, n - hexane, formic acid, Tween - 80, hydrogen peroxide, aqueous sodium carbonate solution and absolute ethanol is 30:450:0.5:1.5:6:15:110;

[0074] Step B2: Add epoxidized ethylene propylene diene monomer rubber into toluene, stir at a speed of 550 rpm for 20 min until uniform, heat up to 65 °C. While stirring, dropwise add a mixed solution c of tetrabutylammonium bromide, 2,6 - pyridinedicarboxylic acid and anhydrous DMF, and control to finish dropping within 15 min. After dropping, continue to stir and react for 6 h, centrifuge, and wash the precipitate with absolute ethanol and deionized water 3 times, and dry at 55 °C to constant weight to obtain the toughening component. Among them, the mass ratio of epoxidized ethylene propylene diene monomer rubber, toluene and mixed solution c is 18:240:52. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, 2,6 - pyridinedicarboxylic acid and anhydrous DMF is 0.5:8:45.

[0075] Examples 1 - 3 and Comparative Examples 1 - 5 provide a kind of high - toughness glass fiber.

[0076] Example 1

[0077] This example provides a kind of high - toughness glass fiber, which includes modified glass fiber, functional solution, functional monomer prepared in Preparation Example 1 and toughening component prepared in Preparation Example 4; The modified glass fiber is prepared from the following raw materials in parts by weight: 46 parts of silicon dioxide, 12 parts of aluminum oxide, 22 parts of calcium oxide, 3.2 parts of boron oxide, 1.2 parts of zinc oxide and 1.8 parts of zirconium oxide;

[0078] The preparation method of this high - toughness glass fiber includes the following steps:

[0079] Step S1: According to the parts by weight, mix the raw materials in the modified glass fiber, melt and draw to prepare the glass fiber blank. Among them, control the melting heating temperature to be set at 1200 °C, keep warm for 4 h, then heat up to 1400 °C at a rate of 10 °C / min, keep warm for 9 h, and set the speed of the drawing machine to 2 m / min;

[0080] Step S2: Cool the glass fiber blank by water to form, then wash it. Set the washing temperature to 28 °C, and then place it at 660 °C for 1.4 h to obtain the glass fiber preform;

[0081] Step S3: Place the glass fiber preform in the etching solution, and then place it under ultrasonic oscillation at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 W for 30 min. Take it out, and then place it in the modification solution. Stir and react at a rotation speed of 550 rpm for 8 h. Wash it 3 times with anhydrous ethanol and deionized water in sequence, and dry it at 60 °C to constant weight to obtain modified glass fiber. Among them, the mass ratio of glass fiber, etching solution, and modification solution is 1:40:20. The etching solution is prepared by mixing ammonium fluoride, 37% hydrochloric acid solution by mass fraction, and deionized water in a mass ratio of 5:3:250. The modification solution is prepared by mixing anhydrous DMF, KH-550, and deionized water in a mass ratio of 35:0.1:2;

[0082] Step S4: Immerse the modified glass fiber in the functional solution, and then add the functional monomer, toughening component, and benzoin dimethyl ether. Stir at a rotation speed of 700 rpm for 12 min until homogeneous. Then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 for 10 min. Control the irradiation temperature at 55 °C, then raise the temperature to 85 °C, maintain the rotation speed unchanged, and continue to stir and react for 0.6 h. Filter and dry at 70 °C to obtain high-tough glass fiber. Among them, the mass ratio of modified glass fiber, functional solution, functional monomer, toughening component, and benzoin dimethyl ether is 1.5:12:0.2:0.4:0.01. The functional solution is prepared by mixing dopamine hydrochloride and Tris-HCl buffer solution in a mass ratio of 2:1000. The pH value of the Tris-HCl buffer solution is 7.5.

[0083] Example 2

[0084] This example provides a high-tough glass fiber, including modified glass fiber, functional solution, functional monomer prepared in Preparation Example 2, and toughening component prepared in Preparation Example 5; The modified glass fiber is prepared from the following raw materials in parts by weight: 54 parts of silicon dioxide, 15 parts of aluminum oxide, 28 parts of calcium oxide, 3.8 parts of boron oxide, 1.7 parts of zinc oxide, and 2.2 parts of zirconium oxide;

[0085] The preparation method of this high-tough glass fiber includes the following steps:

[0086] Step S1: Mix the raw materials in the modified glass fiber according to parts by weight, and melt and draw to prepare a glass fiber preform. Among them, control the heating temperature of melting to be set at 1250 °C, keep it warm for 4.5 h, then raise the temperature to 1450 °C at a rate of 10 °C / min, keep it warm for 10 h, and set the speed of the drawing machine at 2.5 m / min;

[0087] Step S2: Cool the glass fiber preform by water to form it, then wash it with water. Set the water washing temperature at 30°C, and then place it at 690°C for 1.6 h to obtain the glass fiber preform;

[0088] Step S3: Place the glass fiber preform in the etching solution, and then place it under ultrasonic oscillation treatment at an ultrasonic frequency of 40 kHz and an ultrasonic power of 550 w for 33 min. Take it out, and then place it in the modification solution. Control the stirring reaction at a rotation speed of 600 rpm for 9 h. Wash it 4 times with absolute ethanol and deionized water in sequence, and dry it at 65°C to constant weight to obtain the modified glass fiber. Among them, the mass ratio of the glass fiber, the etching solution, and the modification solution is 1:50:25. The etching solution is composed of ammonium fluoride, a hydrochloric acid solution with a mass fraction of 37% and deionized water mixed according to the mass ratio of 5:3:275. The modification solution is composed of anhydrous DMF, KH-550 and deionized water mixed according to the mass ratio of 35:0.15:2;

[0089] Step S4: Immerse the modified glass fiber in the functional solution, then add the functional monomer, the toughening component and benzoin dimethyl ether. Control the stirring at a rotation speed of 750 rpm for 16 min until it is uniform, and then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 irradiate for 15 min. Control the irradiation temperature at 60°C, then raise the temperature to 90°C, maintain the rotation speed unchanged, and continue stirring and reacting for 0.8 h. Filter and dry at 75°C to obtain the high-tough glass fiber. Among them, the mass ratio of the modified glass fiber, the functional solution, the functional monomer, the toughening component and benzoin dimethyl ether is 1.5:14:0.3:0.5:0.02. The functional solution is composed of dopamine hydrochloride and Tris-HCl buffer solution mixed according to the mass ratio of 6:1000. The pH value of the Tris-HCl buffer solution is 8.0.

[0090] Example 3

[0091] This example provides a high-tough glass fiber, including modified glass fiber, functional solution, the functional monomer prepared in Preparation Example 3 and the toughening component prepared in Preparation Example 6; the modified glass fiber is prepared from the following raw materials in parts by weight: 62 parts of silicon dioxide, 18 parts of alumina, 34 parts of calcium oxide, 4.6 parts of boron oxide, 2.2 parts of zinc oxide and 2.6 parts of zirconium oxide;

[0092] The preparation method of this high-tough glass fiber includes the following steps:

[0093] Step S1: Mix the raw materials in the modified glass fiber according to parts by weight, and melt and draw to prepare the glass fiber preform. Among them, control the melting heating temperature at 1300°C, keep it warm for 5 h, then raise the temperature to 1500°C at a rate of 10°C / min, keep it warm for 11 h, and set the speed of the drawing machine at 3 m / min;

[0094] Step S2: Cool the glass fiber preform by water to form a shape, then wash it with water at a washing temperature of 32°C, and then place it at 720°C for 1.8 h to obtain a glass fiber preform;

[0095] Step S3: Place the glass fiber preform in a corrosion solution, and then place it under ultrasonic oscillation treatment at an ultrasonic frequency of 45 kHz and an ultrasonic power of 600 W for 36 min. Take it out, and then place it in a modification solution. Stir and react at a rotation speed of 650 rpm for 10 h. Wash it 5 times with anhydrous ethanol and deionized water in sequence, and dry it at 70°C to constant weight to obtain modified glass fiber. Among them, the mass ratio of glass fiber, corrosion solution, and modification solution is 1:60:30. The corrosion solution is composed of ammonium fluoride, a hydrochloric acid solution with a mass fraction of 37%, and deionized water mixed according to a mass ratio of 5:3:300. The modification solution is composed of anhydrous DMF, KH-550, and deionized water mixed according to a mass ratio of 35:0.2:2;

[0096] Step S4: Immerse the modified glass fiber in a functional solution, then add a functional monomer, a toughening component, and benzoin dimethyl ether. Stir at a rotation speed of 800 rpm for 20 min until uniform, and then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 for 20 min. Control the irradiation temperature at 65°C, then raise the temperature to 95°C, stir and react for 1.0 h, filter, and dry to obtain high-tough glass fiber. Among them, the mass ratio of modified glass fiber, functional solution, functional monomer, toughening component, and benzoin dimethyl ether is 1.5:16:0.4:0.6:0.03. The functional solution is composed of dopamine hydrochloride and Tris-HCl buffer solution mixed according to a mass ratio of 10:1000. The pH value of the Tris-HCl buffer solution is 8.5.

[0097] Comparative Example 1

[0098] This comparative example provides a high-tough glass fiber, including modified glass fiber, functional solution, a functional monomer prepared in Comparative Preparation Example 1, and a toughening component prepared in Preparation Example 4; the modified glass fiber is prepared from the following raw materials in parts by weight: 46 parts of silica, 12 parts of alumina, 22 parts of calcium oxide, 3.2 parts of boron oxide, 1.2 parts of zinc oxide, and 1.8 parts of zirconium oxide;

[0099] The preparation method of this high-tough glass fiber includes the following steps:

[0100] Step S1: Mix the raw materials in the modified glass fiber according to parts by weight, and melt and draw to prepare a glass fiber preform. Among them, control the heating temperature of melting to be set at 1200°C, keep it warm for 4 h, then raise the temperature to 1400°C at a rate of 10°C / min, keep it warm for 9 h, and set the speed of the drawing machine at 2 m / min;

[0101] Step S2: Cool the glass fiber preform by water to form a shape, then wash it with water. Set the water washing temperature at 28 °C, and then place it at 660 °C for 1.4 h to obtain a glass fiber preform;

[0102] Step S3: Place the glass fiber preform in the etching solution, and then place it under ultrasonic oscillation at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 w for 30 min. Take it out, and then place it in the modification solution. Stir and react at a controlled rotation speed of 550 rpm for 8 h. Wash it 3 times with absolute ethanol and deionized water in sequence, and dry it at 60 °C to constant weight to obtain modified glass fibers. Among them, the mass ratio of glass fiber, etching solution, and modification solution is 1:40:20. The etching solution is prepared by mixing ammonium fluoride, 37% hydrochloric acid solution by mass fraction, and deionized water in a mass ratio of 5:3:250. The modification solution is prepared by mixing anhydrous DMF, KH-550, and deionized water in a mass ratio of 35:0.1:2;

[0103] Step S4: Immerse the modified glass fibers in the functional solution, then add the functional monomer, toughening component, and dimethyl benzyl ketone. Stir at a controlled rotation speed of 700 rpm for 12 min until homogeneous, and then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 irradiate for 10 min, control the irradiation temperature at 55 °C, then raise the temperature to 85 °C, stir and react for 0.6 h, filter, and dry to obtain high-tough glass fibers. Among them, the mass ratio of modified glass fiber, functional solution, functional monomer, toughening component, and dimethyl benzyl ketone is 1.5:12:0.2:0.4:0.01. The functional solution is prepared by mixing dopamine hydrochloride and Tris-HCl buffer solution in a mass ratio of 2:1000. The pH value of the Tris-HCl buffer solution is 7.5.

[0104] Comparative Example 2

[0105] This comparative example provides a high-tough glass fiber, including modified glass fibers, a functional solution, a functional monomer prepared in Comparative Preparation Example 2, and a toughening component prepared in Preparation Example 4; The modified glass fibers are prepared from the following raw materials in parts by weight: 46 parts of silica, 12 parts of alumina, 22 parts of calcium oxide, 3.2 parts of boron oxide, 1.2 parts of zinc oxide, and 1.8 parts of zirconium oxide;

[0106] The preparation method of this high-tough glass fiber includes the following steps:

[0107] Step S1: Mix the raw materials in the modified glass fiber by weight, and melt and draw to prepare a glass fiber preform. Among them, control the melting heating temperature at 1200 °C, keep it warm for 4 h, then raise the temperature to 1400 °C at a rate of 10 °C / min, keep it warm for 9 h, and set the speed of the drawing machine at 2 m / min;

[0108] Step S2: Cool the glass fiber preform by water to form it, then wash it with water. Set the water washing temperature at 28 °C, and then place it at 660 °C for 1.4 h to obtain the glass fiber preform.

[0109] Step S3: Place the glass fiber preform in the etching solution, and then place it under ultrasonic oscillation treatment at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 w for 30 min. Take it out, and then place it in the modification solution. Control the stirring reaction at a rotation speed of 550 rpm for 8 h. Wash it 3 times with anhydrous ethanol and deionized water in sequence, and dry it at 60 °C to constant weight to obtain the modified glass fiber. Among them, the mass ratio of the glass fiber, the etching solution, and the modification solution is 1:40:20. The etching solution is prepared by mixing ammonium fluoride, 37% hydrochloric acid solution by mass fraction, and deionized water in a mass ratio of 5:3:250. The modification solution is prepared by mixing anhydrous DMF, KH-550, and deionized water in a mass ratio of 35:0.1:2.

[0110] Step S4: Immerse the modified glass fiber in the functional solution, then add the functional monomer, the toughening component, and benzoin dimethyl ether. Control the stirring at a rotation speed of 700 rpm for 12 min until it is uniform. Then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 irradiate for 10 min, control the irradiation temperature at 55 °C, then raise the temperature to 85 °C, maintain the rotation speed unchanged, and continue stirring and reacting for 0.6 h. Filter and dry it at 70 °C to obtain the high-toughness glass fiber. Among them, the mass ratio of the modified glass fiber, the functional solution, the functional monomer, the toughening component, and benzoin dimethyl ether is 1.5:12:0.2:0.4:0.01. The functional solution is prepared by mixing dopamine hydrochloride and Tris-HCl buffer solution in a mass ratio of 2:1000. The pH value of the Tris-HCl buffer solution is 7.5.

[0111] Comparative Example 3

[0112] This comparative example provides a high-toughness glass fiber, including modified glass fiber, functional solution, functional monomer prepared in Preparation Example 1, and toughening component prepared in Comparative Preparation Example 3; the modified glass fiber is prepared from the following raw materials in parts by weight: 46 parts of silica, 12 parts of alumina, 22 parts of calcium oxide, 3.2 parts of boron oxide, 1.2 parts of zinc oxide, and 1.8 parts of zirconium oxide.

[0113] The preparation method of this high-toughness glass fiber includes the following steps:

[0114] Step S1: Mix the raw materials in the modified glass fiber according to parts by weight, and melt and draw to prepare the glass fiber preform. Among them, control the heating temperature of melting at 1200 °C, keep it warm for 4 h, then raise the temperature to 1400 °C at a rate of 10 °C / min, keep it warm for 9 h, and set the speed of the drawing machine at 2 m / min.

[0115] Step S2: Cool the glass fiber preform by water to form it, then wash it with water at a washing temperature of 28°C, and then place it at 660°C for 1.4 h to obtain a glass fiber preform;

[0116] Step S3: Place the glass fiber preform in the etching solution, and then place it under ultrasonic oscillation treatment at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 w for 30 min. Take it out, and then place it in the modification solution. Stir and react at a controlled rotation speed of 550 rpm for 8 h, wash it 3 times with absolute ethanol and deionized water in sequence, and dry it to constant weight at 60°C to obtain modified glass fiber. Among them, the mass ratio of glass fiber, etching solution, and modification solution is 1:40:20. The etching solution is composed of ammonium fluoride, 37% hydrochloric acid solution by mass fraction, and deionized water mixed according to the mass ratio of 5:3:250. The modification solution is composed of anhydrous DMF, KH-550, and deionized water mixed according to the mass ratio of 35:0.1:2;

[0117] Step S4: Immerse the modified glass fiber in the functional solution, then add the functional monomer, toughening component, and dimethyl benzylidene acetal. Stir at a controlled rotation speed of 700 rpm for 12 min until it is uniform, and then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 irradiate for 10 min, control the irradiation temperature at 55°C, then raise the temperature to 85°C, maintain the rotation speed unchanged, continue to stir and react for 0.6 h, filter, and dry at 70°C to obtain high-tough glass fiber. Among them, the mass ratio of modified glass fiber, functional solution, functional monomer, toughening component, and dimethyl benzylidene acetal is 1.5:12:0.2:0.4:0.01. The functional solution is composed of dopamine hydrochloride and Tris-HCl buffer solution mixed according to the mass ratio of 2:1000. The pH value of the Tris-HCl buffer solution is 7.5.

[0118] Comparative Example 4

[0119] This comparative example provides a high-tough glass fiber, including modified glass fiber, functional solution, functional monomer prepared in Preparation Example 1, and toughening component prepared in Comparative Preparation Example 4; the modified glass fiber is prepared from the following raw materials in parts by weight: 46 parts of silica, 12 parts of alumina, 22 parts of calcium oxide, 3.2 parts of boron oxide, 1.2 parts of zinc oxide, and 1.8 parts of zirconium oxide;

[0120] The preparation method of this high-tough glass fiber includes the following steps:

[0121] Step S1: Mix the raw materials in the modified glass fiber according to parts by weight, melt and draw to prepare a glass fiber preform. Among them, control the melting heating temperature to be set at 1200°C, keep it warm for 4 h, then raise the temperature to 1400°C at a rate of 10°C / min, keep it warm for 9 h, and set the speed of the drawing machine to 2 m / min;

[0122] Step S2: Cool the glass fiber preform by water to form it, then wash it with water. Set the water washing temperature at 28°C, and then place it at 660°C for 1.4 h to obtain the glass fiber preform;

[0123] Step S3: Place the glass fiber preform in the etching solution, and then place it under ultrasonic oscillation treatment at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 w for 30 min. Take it out, and then place it in the modification solution. Stir and react at a rotation speed of 550 rpm for 8 h, wash it 3 times with anhydrous ethanol and deionized water in sequence, and dry it at 60°C to constant weight to obtain the modified glass fiber. Among them, the mass ratio of the glass fiber, the etching solution, and the modification solution is 1:40:20. The etching solution is prepared by mixing ammonium fluoride, a hydrochloric acid solution with a mass fraction of 37% and deionized water according to a mass ratio of 5:3:250. The modification solution is prepared by mixing anhydrous DMF, KH-550 and deionized water according to a mass ratio of 35:0.1:2;

[0124] Step S4: Immerse the modified glass fiber in the functional solution, then add the functional monomer, the toughening component and benzoin dimethyl ether, stir at a rotation speed of 700 rpm for 12 min until it is uniform, and then place it under ultraviolet light with a peak wavelength of 365 nm and an intensity of 80 mw / cm 2 irradiate for 10 min, control the irradiation temperature at 55°C, then raise the temperature to 85°C, keep the rotation speed unchanged, continue to stir and react for 0.6 h, filter, and dry at 70°C to obtain the high-tough glass fiber. Among them, the mass ratio of the modified glass fiber, the functional solution, the functional monomer, the toughening component and benzoin dimethyl ether is 1.5:12:0.2:0.4:0.01. The functional solution is prepared by mixing hydrochloric acid dopamine and Tris-HCl buffer solution according to a mass ratio of 2:1000. The pH value of the Tris-HCl buffer solution is 7.5.

[0125] Performance Test

[0126] Take the glass fibers with a diameter of 5 μm obtained in Examples 1-3 and Comparative Examples 1-4 above, test the tensile strength according to the ASTM D3039 / D3039M standard, and take the glass fibers in Examples 1-5 and Comparative Examples 1-4 to weave fabrics on a loom, and evaluate the friction and wear performance of the materials on an MM-200 type friction and wear testing machine with reference to GB3960-83. The test results are shown in Table 1:

[0127] Table 1 Toughness and wear resistance tests of the glass fibers prepared in Examples 1-3 and Comparative Examples 1-4

[0128]

[0129] As can be seen from Table 1, compared with Comparative Examples 1-4, the high-tough glass fibers prepared in Examples 1-3 have more excellent toughness and wear resistance.

[0130] This specific embodiment is only an interpretation of the present application and does not limit the present application. After reading this specification, those skilled in the art can make modifications to this embodiment that do not contribute creatively as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A high-tenacity glass fiber, characterized in that, It includes modified glass fiber, functional solution, functional monomer and toughening component; the modified glass fiber is prepared from the following raw materials in parts by weight: 46-62 parts of silicon dioxide, 12-18 parts of aluminum oxide, 22-34 parts of calcium oxide, 3.2-4.6 parts of boron oxide, 1.2-2.2 parts of zinc oxide and 1.8-2.6 parts of zirconium oxide; The functional solution is prepared by mixing dopamine hydrochloride and Tris-HCl buffer in a mass ratio of 2-10:1000; The functional monomer is first prepared by hydrolyzing titanium chloride under the dispersion of dodecyl dimethyl hydroxypropyl sulfobetaine to obtain modified nano-titanium dioxide, then hydrolytically coating with tetraethyl orthosilicate to obtain core-shell particles, modifying with KH-550 to obtain amino-functionalized core-shell particles, and finally reacting with 3,3'-dithiodipropionic acid through amidation reaction to obtain dithiol monomer, and finally reacting with allyl glycidyl ether through ring-opening esterification reaction; The toughening component is first prepared by oxidizing ethylene propylene diene monomer rubber with formic acid and hydrogen peroxide to obtain epoxidized ethylene propylene diene monomer rubber, and then reacting with 4-mercaptopyridine dicarboxylic acid through ring-opening esterification reaction; 2. The high-toughness glass fiber according to claim 1, wherein The functional monomer is prepared by the following steps: Step A1: Add titanium chloride and deionized water to anhydrous ethanol, stir evenly, heat up to 35-45 °C, add dodecyl dimethyl hydroxypropyl sulfobetaine while stirring, then heat up to 112-124 °C, stir and react for 6-8 h. After the reaction is completed, cool to room temperature, centrifuge, precipitate, wash and dry to obtain modified nano-titanium dioxide. Then add it to cyclohexane, stir until uniform, adjust the pH value to 8.6-9.2, add tetraethyl orthosilicate, heat up to 58-64 °C, continue to stir for 5-8 h. After the reaction is completed, adjust the pH to neutral, centrifuge, precipitate, wash and dry to obtain core-shell particles; Step A2: Ultrasonically mix the core-shell particles, deionized water, anhydrous ethanol and KH-550 evenly, heat up to 48-56 °C, continue to stir for 5.2-5.8 h, centrifuge, wash and dry to obtain amino-functionalized core-shell particles. Add the amino-functionalized core-shell particles to anhydrous DMF, stir evenly, dropwise add the mixed solution a of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiodipropionic acid and anhydrous DMF. After dropping, heat up to 78-82 °C, stir and react for 2.4-2.8 h. After the reaction is completed, centrifuge, precipitate, wash and dry to obtain dithiol monomer; Step A3: Add the dithiol monomer to anhydrous DMF, heat up to 45-55 °C, stir evenly, adjust the pH to 9-10, dropwise add the mixed solution b of allyl glycidyl ether and isopropyl alcohol while stirring, control to finish dropping within 30 min. After dropping, heat up to 76-82 °C, continue to stir and react for 8-12 h, adjust the pH to neutral, rotary evaporate, wash and dry to obtain functional monomer.

3. A high-tenacity glass fiber according to claim 2, wherein In the step A1, the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyl dimethyl hydroxypropyl sulfobetaine is 3-4:26-40:56-64:0.12-0.16, and the mass ratio of modified nano-titanium dioxide, cyclohexane and tetraethyl orthosilicate is 2.2-2.8:60-80:0.46-0.

52.

4. A high-toughness glass fiber according to claim 2, characterized in that, In the step A2, the mass ratio of the core-shell particles, deionized water, absolute ethanol and KH-550 is 2.4-3.2:11-13:22-30:0.16-0.30, and the mass ratio of the aminated core-shell particles, anhydrous DMF and the mixed solution a is 2.2:40-50:

16. In the mixed solution a, the mass ratio of N,N'-dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 3,3'-dithiobispropionic acid and anhydrous DMF is 0.40-0.48:0.20-0.24:0.36-0.44:

10.

5. The high-tenacity glass fiber according to claim 2, characterized in that, In the step A3, the mass ratio of the dithiol monomer, anhydrous DMF and the mixed solution b is 2-4:36-42:15-25.

6. A high-tenacity glass fiber according to claim 5, characterized in that, In the mixed solution b, the mass ratio of allyl glycidyl ether and isopropanol is 1.2-1.6:12-22.

7. A high-toughness glass fiber according to claim 1, wherein, The toughening component is prepared by the following steps: Step B1: Add ethylene propylene diene monomer (EPDM) into n-hexane, stir to dissolve, heat up to 45-55 °C, then add formic acid and Tween-80, stir evenly, dropwise add hydrogen peroxide, control to finish dropping within 30 min. After dropping, stir and react for 8-10 h. After the reaction ends, add sodium carbonate aqueous solution, continue to stir for 10-12 min, stand for 15-25 min, wash, then add into absolute ethanol, flocculate and precipitate for 2-3 h, dry to obtain epoxidized ethylene propylene diene monomer. Step B2: Add the epoxy group-containing ethylene propylene diene monomer into toluene, stir evenly, heat up to 65-75 °C, while stirring, dropwise add the mixed solution c of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF, control to finish dropping within 15 min. After dropping, continue to stir and react for 6-8 h, centrifuge, wash and dry the precipitate to obtain the toughening component.

8. A high-tenacity glass fiber according to claim 7, characterized in that, In the step B1, the mass ratio of ethylene propylene diene monomer, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and absolute ethanol is 30:450-550:0.5-0.6:1.5-2.5:6-8:15-25:110-120, and the mass fraction of the sodium carbonate aqueous solution is 0.04-0.08%.

9. A high-tenacity glass fiber according to claim 7, wherein In the step B2, the mass ratio of the epoxy group-containing ethylene propylene diene monomer, toluene and the mixed solution c is 18-22:240-260:52-64. In the mixed solution c, the mass ratio of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF is 0.5-0.8:8-10:45-55.

10. A method for preparing the high-toughness glass fiber according to any one of claims 1-9, characterized in that, It includes the following steps: Step S1: Mix the raw materials in the modified glass fiber by weight, and melt and draw to prepare a glass fiber blank. Step S2: Cool and form the glass fiber blank, then wash it with water, and then perform heat treatment to obtain a glass fiber preform. Step S3: Place the glass fiber preform in the etching solution, perform ultrasonic oscillation treatment, take it out, then place it in the modification solution, stir and react for 8-10 h, wash and dry to obtain the modified glass fiber. Step S4: Immerse the modified glass fiber in the functional solution, then add the functional monomer, toughening component and dimethyl benzoin ether, stir evenly, irradiate with ultraviolet light for 10 - 20 min, control the irradiation temperature at 55 - 65 °C, then raise the temperature to 85 - 95 °C, stir and react for 0.6 - 1.0 h, filter, dry, and obtain the high-toughness glass fiber.

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