A high tenacity glass fiber and a method of making the same

Abstract

The application relates to the technical field of glass fibers, and specifically discloses a high-toughness glass fiber and a preparation method thereof, which comprises 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 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 monomer and the toughening component are added in the application, the functional component is composed of a core-shell structure modified by allyl glycidyl ether, the outer layer of the core-shell structure is an amino-silica structure containing a flexible alkyl long chain and a modified silica structure obtained by chemical bonding of 3,3'-dithiodipropionic acid, and the inner core is modified nano-titanium dioxide; the toughening component contains a ternary ethylene-propylene rubber structure, a pyridyl group, a mercapto group and a carboxyl group, and through the action of various structures, the toughness and wear resistance of the glass fiber are improved.

Description

TECHNICAL FIELD

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

[0002] Glass fibers have excellent electrical insulation, excellent high-temperature stability, good corrosion resistance, and high mechanical strength, and are widely used as reinforcing materials in composite materials in the fields of shipbuilding, electronics and electrical appliances, and chemical engineering.

[0003] With the continuous increase in the size of composite products, people have increasingly high requirements for the performance of glass fibers. However, glass fibers are generally brittle and tough, and the existing technology often uses electrostatic compounding to coat carbon nanotubes on the surface of the glass fibers by using the interaction between the carbon nanotubes and the surface charge of the glass fibers to improve the toughness of the glass fibers. However, the carbon nanotubes and the glass fibers in the composite fibers obtained by this method only have weak hydrogen bond interactions, and problems such as uneven distribution and agglomeration of the carbon nanotubes on the surface of the glass fibers can also lead to insignificant reinforcing effect. In addition, the wear resistance of existing glass fibers is poor, which cannot meet the requirements of special fields such as light military weapons, aviation parts, special-purpose automobile parts, 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

[0006] In order to solve the problems of the existing technology that the glass fibers are generally brittle and tough, the existing technology cannot solve the problems of 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, which cannot meet the requirements of special fields, the present application provides a high-toughness glass fiber and a preparation method thereof.

[0007] A 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: 46-62 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.

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

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

[0010] Step S2, the glass fiber roughing is cooled and formed, then washed with water, and then heat treated to obtain a glass fiber preform;

[0011] Step S3, the glass fiber preform is placed in an etching solution, treated by ultrasonic oscillation, taken out, then placed in a modification solution, stirred and reacted for 8-10 hours, washed and dried to obtain modified glass fiber, wherein the mass ratio of the glass fiber, the etching solution and the modification solution is 1:40-60:20-30;

[0012] Step S4, the modified glass fiber is immersed in a functional solution, then functional monomers, toughening components and benzoin dimethyl ether are added, stirred uniformly, irradiated by ultraviolet light for 10-20 minutes, the irradiation temperature is controlled at 55-65℃, then the temperature is increased to 85-95℃, stirred and reacted for 0.6-1.0 hours, filtered and dried to obtain high-toughness glass fiber, wherein the mass ratio of the modified glass fiber, the functional solution, the functional monomers, the toughening components and the 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 melting heating temperature is set to 1200-1300℃, the temperature is kept for 4-5 hours, then the temperature is increased to 1400-1500℃ at a rate of 10℃ / min, the temperature is kept for 9-11 hours, and the speed of the drawing machine is set to 2-3m / min.

[0014] Preferably, in step S2, the glass fiber roughing is cooled and formed by water, the water washing temperature is 28-32℃, the heat treatment temperature is 660-720℃, and the heat treatment time is 1.4-1.8 hours.

[0015] Preferably, in step S3, the etching solution is prepared by mixing ammonium fluoride, 37% hydrochloric acid solution and deionized water at a mass ratio of 5:3:250-300.

[0016] Preferably, in step S4, the functional solution is prepared by mixing dopamine hydrochloride and Tris-HCl buffer solution at a 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 prepared by mixing anhydrous DMF, KH-550 and deionized water at a mass ratio of 35:0.1-0.2:2.

[0018] Preferably, the functional monomers are prepared by the following steps:

[0019] Step A1, titanium chloride and deionized water are added into anhydrous ethanol, stirred uniformly, heated to 35-45℃, while stirring, dodecyl dimethyl hydroxy propyl sulfobetaine is added, then heated to 112-124℃, stirred for 6-8h, after the reaction is completed, cooled to room temperature, centrifugal precipitation, washed and dried, to obtain modified nano titanium dioxide, then it is added into cyclohexane, stirred until uniform, adjust the pH value to 8.6-9.2, then add tetraethyl orthosilicate, heated to 58-64℃, continue to stir for 5-8h, after the reaction is completed, adjust the pH to neutral, centrifugal precipitation, washed and dried, to obtain core-shell particles, wherein the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyl dimethyl hydroxy propyl sulfobetaine is 3-4: 26-40: 56-64: 0.12-0.16, the mass ratio of modified nano titanium dioxide, cyclohexane and tetraethyl orthosilicate is 2.2-2.8: 60-80: 0.46-0.52, in the above reaction process, first, the modified nano titanium dioxide is prepared by LSS method, then the core-shell particles are obtained by coating the modified nano titanium dioxide with tetraethyl orthosilicate as a silicon source;

[0020] Step A2, the core-shell particles, deionized water, anhydrous ethanol and KH-550 are ultrasonically mixed uniformly, heated to 48-56℃, continue to stir for 5.2-5.8h, centrifugal washed and dried, to obtain aminated core-shell particles, then the aminated core-shell particles are added into anhydrous DMF, stirred uniformly, drop the mixed solution a of N, N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3, 3'-dithiodipropionic acid and anhydrous DMF, after dropping, heated to 78-82℃, stirred for 2.4-2.8h, after the reaction is completed, centrifugal precipitation, washed and dried, to obtain dithio monomer; wherein the mass ratio of core-shell particles, deionized water, anhydrous ethanol and KH-550 is 2.4-3.2: 11-13: 22-30: 0.16-0.30, the mass ratio of aminated core-shell particles, anhydrous DMF and mixed solution a is 2.2: 40-50: 16, in the mixed solution a, the mass ratio of N, N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3, 3'-dithiodipropionic acid and anhydrous DMF is 0.40-0.48: 0.20-0.24: 0.36-0.44: 10, first, the core-shell particles are treated with KH-550 to obtain aminated core-shell particles, the carboxyl group of 3, 3'-dithiodipropionic acid can be grafted on the surface of aminated core-shell particles by amide reaction with the amino group on the surface of aminated core-shell particles, which reduces the agglomeration of core-shell particles, improves the dispersion performance of core-shell particles and improves the compatibility of core-shell particles, at the same time, the remaining carboxyl group of dithio monomer can also participate in the subsequent reaction process;

[0021] Step A3, the dithio monomer is added into anhydrous DMF, warmed to 45-55℃, stirred uniformly, adjusted to pH 9-10, dropwise added the mixed solution b of allyl glycidyl ether and isopropyl alcohol while stirring, controlled to be dropped within 30 min, after dropping, warmed to 76-82℃, continue to stir for 8-12 h, adjust the pH to neutral, rotary evaporation, washing and drying, to obtain the functional monomer, wherein the mass ratio of dithio monomer, anhydrous DMF and mixed solution b is 2-4:36-42:15-25, the mass ratio of allyl glycidyl ether and isopropyl alcohol in mixed solution b is 1.2-1.6:12-22, in the above reaction process, the carboxyl group on the dithio monomer and the epoxy group on the allyl glycidyl ether undergo ring-opening esterification reaction to obtain the functional monomer.

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

[0023] Step B1, the terpolymer is added into n-hexane, stirred and dissolved, warmed to 45-55℃, then formic acid and Tween-80 are added, stirred uniformly, dropwise added hydrogen peroxide, controlled to be dropped within 30 min, after dropping, stirred for 8-10 h, after the reaction, sodium carbonate aqueous solution is added, continue to stir for 10-12 min, stand for 15-25 min, washed, then added into anhydrous ethanol, flocculation and precipitation for 2-3 h, dried, to obtain the epoxidized terpolymer, wherein the mass ratio of terpolymer, 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, the mass fraction of sodium carbonate aqueous solution is 0.04-0.08%;

[0024] Step B2, the epoxy terpolymer is added into toluene, stirred uniformly, warmed to 65-75℃, dropwise added the mixed solution c of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF while stirring, controlled to be dropped within 15 min, after dropping, continue to stir for 6-8 h, centrifuged, the precipitate is washed and dried, to obtain the toughening component, wherein the mass ratio of epoxy terpolymer, toluene and mixed solution c is 18-22:240-260:52-64, the mass ratio of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF in mixed solution c is 0.5-0.8:8-10:45-55, in the above reaction process, toluene is used as the solvent, tetrabutylammonium bromide is used as the catalyst, 4-mercaptopyridine dicarboxylic acid and epoxy terpolymer undergo ring-opening esterification reaction 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 the glass fiber, the application starts from two aspects, one is to add a toughening component, the toughening component contains a ternary ethylene-propylene rubber structure, a pyridyl group, a mercapto group and a carboxyl group, the presence of the ternary ethylene-propylene rubber structure has good wear resistance, the epoxy group grafted thereon not only can be chemically bonded with the amino group on the polydopamine in the functional solution, further improving the toughness of the glass fiber, and the epoxy group as a strong polar side group can improve the compatibility between the ternary ethylene-propylene rubber 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 the polydopamine in the functional solution, further improving the toughness of the glass fiber, the presence of the mercapto group can be chemically bonded with the unsaturated double bond on the functional monomer, further improving the toughness of the glass fiber, and the presence of the carboxyl group can be used as an anchoring point to undergo ring-opening reaction with the epoxy group of the functional monomer, further improving the crosslinking degree and improving the toughness of the glass fiber; the other is to add a functional monomer, the functional monomer 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 amino-containing 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, can improve the wear resistance of the glass fiber together with the nano titanium dioxide, and the dynamic disulfide bond grafted thereon can improve the self-repairing performance of the functional monomer, further improving the wear resistance and toughness of the glass fiber, and the introduction of the functional monomer into the glass fiber can play a synergistic effect with the toughening component and improve the toughness and wear resistance of the glass fiber together. DETAILED DESCRIPTION

[0027] In order to make the embodiments of the application easier to understand, the application will be described in detail below in combination with specific examples, which only serve to illustrate the application and are not limited to the scope of the application.

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

[0029] Preparation Example 1

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

[0031] Step A1, titanium chloride and deionized water were added into anhydrous ethanol, stirred at 500 rpm for 16 min until uniform, heated to 35℃, while stirring, added dodecyl dimethyl hydroxy propyl sulfobetaine, then heated to 112℃, maintained the same speed, continued to stir for 6h, after the reaction was completed, cooled to room temperature, centrifugal precipitation, then washed with anhydrous ethanol and deionized water for 3 times, dried at 55℃ until constant weight, obtained modified nano titanium dioxide, then added into cyclohexane, stirred at 500 rpm for 25 min until uniform, adjusted pH to 8.6 with 0.4M sodium hydroxide aqueous solution, then added tetraethyl orthosilicate, heated to 58℃, continued to stir for 5h, after the reaction was completed, adjusted pH to neutral with 0.3M hydrochloric acid aqueous solution, centrifugal precipitation, then washed with anhydrous ethanol and deionized water for 3 times, dried at 60℃ until constant weight, obtained core-shell particles, wherein the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyl dimethyl hydroxy propyl sulfobetaine was 3:26:56:0.12, the mass ratio of modified nano titanium dioxide, cyclohexane and tetraethyl orthosilicate was 2.2:60:0.46;

[0032] Step A2, the core-shell particles, deionized water, anhydrous ethanol and KH-550 were ultrasonically treated at 35kHz, 500w for 40 min until uniform, heated to 48℃, continued to stir for 5.2h, centrifugal, then washed with anhydrous ethanol and deionized water for 3 times, dried at 50℃ until constant weight, obtained aminated core-shell particles, then added into anhydrous DMF, controlled the stirring speed at 550 rpm for 15 min until uniform, added dropwise a mixture a of N,N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3,3'-dithiodipropionic acid and anhydrous DMF, after dropwise, heated to 78℃, stirred for 2.4h, after the reaction was completed, centrifugal, then washed with anhydrous ethanol and deionized water for 3 times, dried at 65℃ until constant weight, obtained dithio monomer, wherein the mass ratio of core-shell particles, deionized water, anhydrous ethanol and KH-550 was 2.4:11:22:0.16, the mass ratio of aminated core-shell particles, anhydrous DMF and mixture a was 2.2:40:16, in the mixture a, the mass ratio of N,N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3,3'-dithiodipropionic acid and anhydrous DMF was 0.4:0.2:0.36:10;

[0033] Step A3, the dithio monomer is added into anhydrous DMF, warmed to 45°C, stirred at 600 rpm for 16 min until uniform, adjusted to pH 9 with 0.6M aqueous sodium hydroxide solution, added dropwise the mixture of allyl glycidyl ether and isopropanol b under stirring, controlled to drop within 30 min, after dropping, warmed to 76°C, maintained the stirring speed, continued to stir for 8 h, adjusted to neutral with 0.8M aqueous hydrochloric acid solution, controlled the rotary evaporation temperature to 82°C, rotary evaporated to remove anhydrous DMF, washed with anhydrous ethanol and deionized water in turn for 3 times, dried at 55°C to constant weight, obtained the functional monomer, wherein the mass ratio of dithio monomer, anhydrous DMF and mixture b is 2:36:15, and the mass ratio of allyl glycidyl ether and isopropanol in mixture b is 1.2:12.

[0034] Preparation Example 2

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

[0036] Step A1, titanium chloride and deionized water are added into anhydrous ethanol, stirred at 600 rpm for 20 min until uniform, warmed to 40°C, added dodecyl dimethyl hydroxypropyl sulfobetaine under stirring, then warmed to 118°C, maintained the stirring speed, continued to stir for 7 h, after the reaction, cooled to room temperature, centrifuged and precipitated, washed with anhydrous ethanol and deionized water in turn for 4 times, dried at 60°C to constant weight, obtained modified nano titanium dioxide, then added into cyclohexane, stirred at 550 rpm for 30 min until uniform, adjusted to pH 8.9 with 0.6M aqueous sodium hydroxide solution, then added tetraethyl orthosilicate, warmed to 61°C, continued to stir for 6.5 h, after the reaction, adjusted to neutral with 0.4M aqueous hydrochloric acid solution, centrifuged and precipitated, washed with anhydrous ethanol and deionized water in turn for 4 times, dried at 65°C to constant weight, obtained core-shell particles, wherein the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyl dimethyl hydroxypropyl sulfobetaine 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, the core-shell particles, deionized water, anhydrous ethanol and KH-550 are uniformly ultrasonicated at an ultrasonic frequency of 30 kHz and an ultrasonic power of 450 w for 45 min, the temperature is raised to 52℃, and the stirring is continued for 5.5 h, then centrifuged, washed with anhydrous ethanol and deionized water in sequence for 4 times, and dried at 54℃ until the weight is constant to obtain the aminated core-shell particles, which are added into anhydrous DMF, and stirred at a speed of 600 rpm for 20 min until uniform, then a mixed solution a of N,N-dicyclohexyl carbodiimide, 4-dimethylaminopyridine, 3,3'-dithiodipropionic acid and anhydrous DMF is added dropwise, after the dropwise addition is completed, the temperature is raised to 105℃, and the stirring is continued for 2.6 h, after the reaction is completed, centrifuged, washed with anhydrous ethanol and deionized water in sequence for 4 times, and dried at 70℃ until the weight is constant to obtain the dithio monomer, wherein the mass ratio of the core-shell particles, deionized water, anhydrous ethanol and KH-550 is 2.8:12:26:0.23, the mass ratio of the aminated core-shell particles, anhydrous DMF and the mixed solution a is 2.2:45:16, and the mass ratio of N,N-dicyclohexyl carbodiimide, 4-dimethylaminopyridine, 3,3'-dithiodipropionic acid and anhydrous DMF in the mixed solution a is 0.44:0.22:0.40:10;

[0038] Step A3, the dithio monomer is added into anhydrous DMF, the temperature is raised to 50℃, and stirred at a speed of 650 rpm for 18 min until uniform, then 0.8M sodium hydroxide aqueous solution is used to adjust the pH to 9.5, a mixed solution b of allyl glycidyl ether and isopropanol is added dropwise while stirring, and the dropwise addition is controlled to be completed within 30 min, after the dropwise addition is completed, the temperature is raised to 79℃, the stirring speed is kept unchanged, and the stirring is continued for 10 h, then 1.0M hydrochloric acid aqueous solution is used to adjust the pH to neutral, the rotary evaporation temperature is controlled to be 84℃, and the rotary evaporation is performed until the anhydrous DMF is removed, then washed with anhydrous ethanol and deionized water in sequence for 4 times, and dried at 60℃ until the weight is constant to obtain the functional monomer, wherein the mass ratio of the dithio monomer, anhydrous DMF and the mixed solution b is 3:39:20, and the mass ratio of allyl glycidyl ether and isopropanol in the mixed solution b is 1.4:18.

[0039] Preparation Example 3

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

[0041] Step A1, titanium chloride and deionized water were added into anhydrous ethanol, stirred for 24 min at 700 rpm until uniform, heated to 45℃, while stirring, added dodecyl dimethyl hydroxy propyl sulfobetaine, then heated to 124℃, stirred for 8 h, after the reaction was completed, cooled to room temperature, centrifuged and precipitated, then washed with anhydrous ethanol and deionized water for 5 times in turn, dried at 65℃ until constant weight, to obtain modified nano titanium dioxide, then added into cyclohexane, stirred for 35 min at 600 rpm until uniform, adjusted pH to 9.2 with 0.8M sodium hydroxide aqueous solution, then added tetraethyl orthosilicate, heated to 64℃, continued to stir for 8 h, after the reaction was completed, adjusted pH to neutral with 0.5M hydrochloric acid aqueous solution, centrifuged and precipitated, then washed with anhydrous ethanol and deionized water for 5 times in turn, dried at 70℃ until constant weight, to obtain core-shell particles, wherein the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyl dimethyl hydroxy propyl sulfobetaine was 4:40:64:0.16, and the mass ratio of modified nano titanium dioxide, cyclohexane and tetraethyl orthosilicate was 2.8:80:0.52;

[0042] Step A2, the core-shell particles, deionized water, anhydrous ethanol and KH-550 were ultrasonically treated for 35 min at 40 kHz and 550 w until uniform, heated to 56℃, continued to stir for 5.8 h, then washed with anhydrous ethanol and deionized water for 5 times in turn, dried at 65℃ until constant weight, to obtain aminated core-shell particles, then added into anhydrous DMF, stirred for 25 min at 650 rpm until uniform, added dropwise a mixture a of N,N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3,3'-dithiodipropionic acid and anhydrous DMF, after dropwise addition, heated to 116℃, stirred for 2.8 h, after the reaction was completed, centrifuged, then washed with anhydrous ethanol and deionized water for 5 times in turn, dried at 75℃ until constant weight, to obtain dithio monomer, wherein the mass ratio of core-shell particles, deionized water, anhydrous ethanol and KH-550 was 3.2:13:30:0.30, the mass ratio of aminated core-shell particles, anhydrous DMF and the mixture a was 2.2:50:16, and the mass ratio of N,N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3,3'-dithiodipropionic acid and anhydrous DMF in the mixture a was 0.48:0.24:0.44:10;

[0043] Step A3, the dithio monomer is added into anhydrous DMF, warmed to 55°C, stirred at a rotation speed of 700 rpm for 20 min to be uniform, adjusted to pH 10 with 1.0M aqueous sodium hydroxide solution, and a mixture of allyl glycidyl ether and isopropanol b is added dropwise while stirring, controlled to be dropped within 30 min, after dropping, warmed to 82°C, maintained the rotation speed unchanged, continued to stir for 12 h, then adjusted to neutral pH with 1.2M aqueous hydrochloric acid solution, controlled the rotary evaporation temperature to be 86°C, rotary evaporated to remove anhydrous DMF, then washed with anhydrous ethanol and deionized water in turn for 5 times, dried at 65°C to constant weight, to obtain the functional monomer, wherein the mass ratio of the dithio monomer, anhydrous DMF and the mixture b is 4:42:25, and the mass ratio of allyl glycidyl ether and isopropanol in the mixture b is 1.6:22.

[0044] Comparative Preparation Example 1

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

[0046] Step A1, titanium chloride and deionized water are added into anhydrous ethanol, stirred at a rotation speed of 500 rpm for 16 min to be uniform, warmed to 35°C, and dodecyl dimethyl hydroxypropyl sulfobetaine is added while stirring, then warmed to 112°C, maintained the rotation speed unchanged, continued to stir for 6 h, after the reaction is completed, cooled to room temperature, centrifuged to precipitate, then washed with anhydrous ethanol and deionized water in turn for 3 times, dried at 55°C to constant weight, to obtain modified nano titanium dioxide, then it is added into cyclohexane, stirred at a rotation speed of 500 rpm for 25 min to be uniform, adjusted to pH 8.6 with 0.4M aqueous sodium hydroxide solution, then tetraethyl orthosilicate is added, warmed to 58°C, continued to stir for 5 h, after the reaction is completed, adjusted to neutral pH with 0.3M aqueous hydrochloric acid solution, centrifuged to precipitate, then washed with anhydrous ethanol and deionized water in turn for 3 times, dried at 60°C to constant weight, to obtain core-shell particles, wherein the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyl dimethyl hydroxypropyl 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;

[0047] Step A2, the core-shell particles, deionized water, anhydrous ethanol and KH-550 were uniformly treated by ultrasonic at an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 w for 40 min, and then the temperature was increased to 48 °C and the stirring was continued for 5.2 h. After centrifugation, the product was washed with anhydrous ethanol and deionized water for 3 times, respectively, and then dried at 50 °C until the weight was constant to obtain the aminated core-shell particles. The aminated core-shell particles were added into anhydrous DMF and stirred at a speed of 550 rpm for 15 min until uniform. Then a mixed solution a of N,N-dicyclohexyl carbodiimide, 4-dimethylaminopyridine, 3,3'-thiodipropionic acid and anhydrous DMF was added dropwise. After the dropwise addition was completed, the temperature was increased to 78 °C and the stirring was continued for 2.4 h. After the reaction was completed, the product was centrifuged, washed with anhydrous ethanol and deionized water for 3 times, respectively, and then dried at 65 °C until the weight was constant to obtain the disulfide monomer. In the process, the mass ratio of the core-shell particles, deionized water, anhydrous ethanol and KH-550 was 2.4:11:22:0.16, the mass ratio of the aminated core-shell particles, anhydrous DMF and the mixed solution a was 2.2:40:16, and the mass ratio of N,N-dicyclohexyl carbodiimide, 4-dimethylaminopyridine, 3,3'-thiodipropionic acid and anhydrous DMF in the mixed solution a was 0.4:0.2:0.36:10.

[0048] Step A3, the disulfide monomer was added into anhydrous DMF, the temperature was increased to 45 °C, and the stirring was continued at a speed of 600 rpm for 16 min until uniform. Then the pH was adjusted to 9 by using a 0.6 M aqueous sodium hydroxide solution, and a mixed solution b of allyl glycidyl ether and isopropanol was added dropwise while stirring. The dropwise addition was controlled to be completed within 30 min. After the dropwise addition was completed, the temperature was increased to 76 °C, the stirring speed was kept unchanged, and the stirring was continued for 8 h. Then the pH was adjusted to neutral by using a 0.8 M aqueous hydrochloric acid solution, the temperature of rotary evaporation was controlled to be 82 °C, and the anhydrous DMF was removed by rotary evaporation. The product was washed with anhydrous ethanol and deionized water for 3 times, respectively, and then dried at 55 °C until the weight was constant to obtain the functional monomer. In the process, the mass ratio of the disulfide monomer, anhydrous DMF and the mixed solution b was 2:36:15, and the mass ratio of allyl glycidyl ether and isopropanol in the mixed solution b was 1.2:12.

[0049] Comparative Preparation Example 2

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

[0051] Step A1, titanium chloride and deionized water were added into anhydrous ethanol, stirred at 500 rpm for 16 min until uniform, heated to 35℃, while stirring, added dodecyl dimethyl hydroxy propyl sulfobetaine, then heated to 112℃, maintained the same speed, continued to stir for 6h, after the reaction was completed, cooled to room temperature, centrifugal precipitation, then washed with anhydrous ethanol and deionized water for 3 times, dried at 55℃ until constant weight, obtained modified nano titanium dioxide, then added into cyclohexane, stirred at 500 rpm for 25 min until uniform, adjusted pH to 8.6 with 0.4M sodium hydroxide aqueous solution, then added tetraethyl orthosilicate, heated to 58℃, continued to stir for 5h, after the reaction was completed, adjusted pH to neutral with 0.3M hydrochloric acid aqueous solution, centrifugal precipitation, then washed with anhydrous ethanol and deionized water for 3 times, dried at 60℃ until constant weight, obtained core-shell particles, wherein the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyl dimethyl hydroxy propyl sulfobetaine was 3:26:56:0.12, the mass ratio of modified nano titanium dioxide, cyclohexane and tetraethyl orthosilicate was 2.2:60:0.46;

[0052] Step A2, the core-shell particles, deionized water, anhydrous ethanol and KH-550 were ultrasonically treated at 35kHz, 500w for 40 min until uniform, heated to 48℃, continued to stir for 5.2h, centrifugal, then washed with anhydrous ethanol and deionized water for 3 times, dried at 50℃ until constant weight, obtained aminated core-shell particles, then added into anhydrous DMF, controlled the stirring speed at 550 rpm for 15 min until uniform, added dropwise a mixture a of N,N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3,3'-dithiodipropionic acid and anhydrous DMF, after dropwise, heated to 78℃, stirred for 2.4h, after the reaction was completed, centrifugal, then washed with anhydrous ethanol and deionized water for 3 times, dried at 65℃ until constant weight, obtained dithio monomer, wherein the mass ratio of core-shell particles, deionized water, anhydrous ethanol and KH-550 was 2.4:11:22:0.16, the mass ratio of aminated core-shell particles, anhydrous DMF and mixture a was 2.2:40:16, in the mixture a, the mass ratio of N,N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3,3'-dithiodipropionic acid and anhydrous DMF was 0.4:0.2:0.36:10;

[0053] Step A3, the dithio monomer was added into anhydrous DMF, warmed to 45℃, stirred at 600rpm for 16min to be uniform, adjusted pH to 9 with 0.6M sodium hydroxide aqueous solution, added dropwise the mixture b of isopropyl glycidyl ether and isopropyl alcohol under stirring, controlled the dropping to be completed within 30min, after dropping, warmed to 76℃, maintained the stirring speed, continued to stir for 8h, adjusted pH to neutral with 0.8M hydrochloric acid aqueous solution, controlled the rotary evaporation temperature to be 82℃, rotary evaporated to remove anhydrous DMF, washed with anhydrous ethanol and deionized water in turn for 3 times, dried at 55℃ to constant weight, obtained the functional monomer, wherein the mass ratio of dithio monomer, anhydrous DMF and mixture b was 2:36:15, and the mass ratio of isopropyl glycidyl ether and isopropyl alcohol in mixture b was 1.2:12.

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

[0055] Preparation Example 4

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

[0057] Step B1, the ethylene-propylene-diene rubber was added into n-hexane, stirred and dissolved, warmed to 45℃, then added formic acid and Tween-80, controlled the stirring speed to be 500rpm for 16min to be uniform, added dropwise hydrogen peroxide under stirring, controlled the dropping to be completed within 30min, after dropping, stirred for 8h, after the reaction, added 0.04% sodium carbonate aqueous solution, continued to stir for 10min, stood for 15min, washed with deionized water for 3 times, then added into anhydrous ethanol, flocculated and precipitated for 2h, dried at 50℃ to constant weight, obtained the epoxidized ethylene-propylene-diene rubber, wherein the mass ratio of ethylene-propylene-diene rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol was 30:450:0.5:1.5:6:15:110;

[0058] Step B2, the epoxy ethylene-propylene-diene rubber was added into toluene, controlled the stirring speed to be 550rpm for 20min to be uniform, warmed to 65℃, added dropwise the mixture c of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF under stirring, controlled the dropping to be completed within 15min, after dropping, continued to stir for 6h, centrifuged, the precipitate was washed with anhydrous ethanol and deionized water for 3 times, dried at 55℃ to constant weight, obtained the toughening component, wherein the mass ratio of epoxy ethylene-propylene-diene rubber, toluene and mixture c was 18:240:52, and the mass ratio of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF in mixture c was 0.5:8:45.

[0059] Preparation Example 5

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

[0061] Step B1, the ternary ethylene propylene rubber is added into n-hexane, stirred and dissolved, heated to 50°C, then formic acid and Tween-80 are added, stirred at a speed of 550 rpm for 20 min to be uniform, hydrogen peroxide is added dropwise, which is controlled to be added dropwise within 30 min, after dropping, stirring reaction is carried out for 9 h, after the reaction is completed, 0.06% sodium carbonate aqueous solution is added, stirring is continued for 11 min, standing is carried out for 20 min, deionized water is washed for 4 times, then anhydrous ethanol is added, flocculation and precipitation are carried out for 2.5 h, drying is carried out at 55°C until the constant weight, and the epoxidized ternary ethylene propylene rubber is obtained, wherein the mass ratio of the ternary ethylene propylene rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 30:500:0.55:2.0:7:20:115;

[0062] Step B2, the epoxy-based ternary ethylene propylene rubber is added into toluene, stirring is carried out at a speed of 600 rpm for 25 min to be uniform, heating is carried out to 70°C, the mixed solution c of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF is added dropwise while stirring, which is controlled to be added dropwise within 15 min, after dropping, stirring reaction is continued for 7 h, centrifugation is carried out, the precipitate is washed with anhydrous ethanol and deionized water for 4 times, and drying is carried out at 60°C until the constant weight, and the toughening component is obtained, wherein the mass ratio of the epoxy-based ternary ethylene propylene rubber, toluene and the mixed solution c is 20:250:58, and 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] The preparation example provides a toughening component, which is prepared by the following steps:

[0065] Step B1, the ternary ethylene propylene rubber is added into n-hexane, stirred and dissolved, heated to 55°C, then formic acid and Tween-80 are added, stirring is carried out at a speed of 600 rpm for 25 min to be uniform, hydrogen peroxide is added dropwise, which is controlled to be added dropwise within 30 min, after dropping, stirring reaction is carried out for 10 h, after the reaction is completed, 0.08% sodium carbonate aqueous solution is added, stirring is continued for 12 min, standing is carried out for 25 min, deionized water is washed for 5 times, then anhydrous ethanol is added, flocculation and precipitation are carried out for 3 h, and drying is carried out at 60°C until the constant weight, and the epoxidized ternary ethylene propylene rubber is obtained, wherein the mass ratio of the ternary ethylene propylene rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 30:550:0.6:2.5:8:25:120;

[0066] Step B2: Add epoxy-based EPDM rubber to toluene and stir at 650 rpm for 30 minutes until homogeneous. Heat to 75°C and add a mixture of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid, and anhydrous DMF dropwise while stirring, controlling the addition to be completed within 15 minutes. After the addition is complete, continue stirring and react for 8 hours. Centrifuge, wash the precipitate five times with anhydrous ethanol and deionized water, and dry at 70°C to constant weight to obtain the toughening component. The mass ratio of epoxy-based EPDM rubber, toluene, and mixture c is 22:260:64, and the mass ratio of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid, and anhydrous DMF in mixture c 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 EPDM rubber to n-hexane, stir to dissolve, heat to 45℃, then add formic acid and Tween-80, and stir at 500 rpm for 16 minutes until homogeneous. While stirring, add hydrogen peroxide dropwise, controlling the addition to be completed within 30 minutes. After the addition is complete, stir and react for 8 hours. After the reaction is complete, add a 0.04% sodium carbonate aqueous solution, continue stirring for 10 minutes, let stand for 15 minutes, wash three times with deionized water, then add anhydrous ethanol, flocculate and precipitate for 2 hours, and dry at 50℃ to constant weight to obtain epoxidized EPDM rubber. The mass ratio of EPDM rubber, n-hexane, formic acid, Tween-80, hydrogen peroxide, sodium carbonate aqueous solution and anhydrous ethanol is 30:450:0.5:1.5:6:15:110.

[0070] Step B2: Add epoxy-based EPDM rubber to toluene and stir at 550 rpm for 20 minutes until homogeneous. Heat to 65°C and add a mixture of tetrabutylammonium bromide, 4-mercaptobenzoic acid, and anhydrous DMF dropwise while stirring, completing the addition within 15 minutes. After addition, continue stirring and react for 6 hours. Centrifuge, wash the precipitate three times with anhydrous ethanol and deionized water, and dry at 55°C to constant weight to obtain the toughening component. The mass ratio of epoxy-based EPDM rubber, toluene, and mixture c is 18:240:52. In mixture 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 the ethylene propylene rubber into the n-hexane, stir and dissolve, heat to 45℃, then add the formic acid and the Tween-80, control the stirring speed at 500 rpm for 16 min until uniform, drop the hydrogen peroxide while stirring, control the dropping time within 30 min, after dropping, stir for 8 h, after the reaction is completed, add the 0.04% sodium carbonate aqueous solution, continue to stir for 10 min, stand for 15 min, wash with deionized water for 3 times, then add into the anhydrous ethanol, flocculate and precipitate for 2 h, dry at 50℃ until constant weight, obtain the epoxidized ethylene propylene rubber, wherein the mass ratio of the ethylene propylene rubber, the n-hexane, the formic acid, the Tween-80, the hydrogen peroxide, the sodium carbonate aqueous solution and the anhydrous ethanol is 30:450:0.5:1.5:6:15:110;

[0074] Step B2, add the epoxy ethylene propylene rubber into the toluene, control the stirring speed at 550 rpm for 20 min until uniform, heat to 65℃, drop the mixture c of the tetrabutylammonium bromide, the 2,6-pyridinedicarboxylic acid and the anhydrous DMF while stirring, control the dropping time within 15 min, after dropping, continue to stir for 6 h, centrifuge, the precipitate is washed with the anhydrous ethanol and the deionized water for 3 times, dry at 55℃ until constant weight, obtain the toughening component, wherein the mass ratio of the epoxy ethylene propylene rubber, the toluene and the mixture c is 18:240:52, in the mixture c, the mass ratio of the tetrabutylammonium bromide, the 2,6-pyridinedicarboxylic acid and the anhydrous DMF is 0.5:8:45.

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

[0076] Example 1

[0077] The present embodiment provides a high-toughness glass fiber, which comprises a modified glass fiber, a functional solution, the functional monomer prepared in Preparation Example 1 and the toughening component prepared in Preparation Example 4; the modified glass fiber is prepared from the following raw materials by weight parts: 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 the high-toughness glass fiber comprises the following steps:

[0079] Step S1, mix the raw materials in the modified glass fiber according to the weight parts, melt and draw to prepare a glass fiber blank, wherein the heating temperature of the melting is set to 1200℃, heat preservation for 4 h, then heat to 1400℃ at a rate of 10℃ / min, heat preservation for 9 h, the speed of the drawing machine is set to 2 m / min;

[0080] Step S2, cool and shape the glass fiber blank by water, then wash with water, the water washing temperature is set to 28℃, then treat at 660℃ for 1.4 h, obtain the glass fiber preform.

[0081] Step S3, the glass fiber preform is placed in the etching liquid, and then is placed in ultrasonic oscillation treatment under the condition of an ultrasonic frequency of 35 kHz and an ultrasonic power of 500 w for 30 min. The glass fiber preform is taken out, and then is placed in the modification liquid and stirred at a rotating speed of 550 rpm for 8 h. The glass fiber preform is washed with anhydrous ethanol and deionized water in sequence for 3 times, and is dried at 60 ℃ until the weight is constant. Thus, the modified glass fiber is obtained. The mass ratio of the glass fiber, the etching liquid and the modification liquid is 1:40:20. The etching liquid is prepared by mixing ammonium fluoride, a 37% hydrochloric acid solution and deionized water in a mass ratio of 5:3:250. The modification liquid is prepared by mixing anhydrous DMF, KH-550 and deionized water in a mass ratio of 35:0.1:2.

[0082] Step S4, the modified glass fiber is immersed in the functional solution, and then the functional monomer, the toughening component and benzoin dimethyl ether are added. The mixture is stirred at a rotating speed of 700 rpm for 12 min until the mixture is uniform. The mixture is irradiated under ultraviolet light with a wavelength peak of 365 nm and an intensity of 80 mw / cm 2 for 10 min. The irradiation temperature is controlled to be 55 ℃. The temperature is increased to 85 ℃, and the rotating speed is kept unchanged. The mixture is continuously stirred for 0.6 h. The mixture is filtered and dried at 70 ℃. Thus, the high-toughness glass fiber is obtained. 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 in a mass ratio of 2:1000. The pH value of the Tris-HCl buffer is 7.5.

[0083] Example 2

[0084] The high-toughness glass fiber provided by the example comprises the modified glass fiber, the functional solution, the functional monomer prepared in the preparation example 2 and the toughening component prepared in the 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 the high-toughness glass fiber comprises the following steps.

[0086] Step S1, the raw materials in the modified glass fiber are mixed in parts by weight. The glass fiber preform is prepared by melt drawing. The heating temperature of the melt is set to be 1250 ℃. The temperature is kept for 4.5 h. The temperature is increased to 1450 ℃ at a rate of 10 ℃ / min. The temperature is kept for 10 h. The speed of the drawing machine is set to be 2.5 m / min.

[0087] Step S2, the glass fiber blank is cooled and shaped by water, then washed by water, the water washing temperature is set to 30℃, then placed in 690℃ for 1.6h, the glass fiber preform is obtained;

[0088] Step S3, the glass fiber preform is placed in the etching solution, then placed in the ultrasonic frequency of 40kHz, ultrasonic power of 550w, ultrasonic oscillation treatment for 33min, then taken out, placed in the modification solution, control the stirring speed to 600rpm, stirring reaction for 9h, washed by anhydrous ethanol and deionized water for 4 times in turn, dried at 65℃ to constant weight, the modified glass fiber is obtained, wherein, the mass ratio of glass fiber, etching solution and modification solution is 1:50:25, the etching solution is mixed by ammonium fluoride, 37% mass fraction hydrochloric acid solution and deionized water according to the mass ratio of 5:3:275, the modification solution is mixed by anhydrous DMF, KH-550 and deionized water according to the mass ratio of 35:0.15:2;

[0089] Step S4, the modified glass fiber is immersed in the functional solution, then the functional monomer, the toughening component and the benzoin dimethyl ether are added, control the stirring speed to 750rpm, stir for 16min to be uniform, then placed in the ultraviolet light with the wavelength peak of 365nm and the intensity of 80mw / cm 2 , irradiate for 15min, control the irradiation temperature to 60℃, then increase the temperature to 90℃, maintain the stirring speed unchanged, continue to stir for 0.8h, filter, dry at 75℃, the high-toughness glass fiber is obtained, wherein, the mass ratio of modified glass fiber, functional solution, functional monomer, toughening component and benzoin dimethyl ether is 1.5:14:0.3:0.5:0.02, the functional solution is mixed by dopamine hydrochloride and Tris-HCl buffer according to the mass ratio of 6:1000, the pH value of Tris-HCl buffer is 8.0.

[0090] Example 3

[0091] The embodiment provides a high-toughness glass fiber, which comprises modified glass fiber, functional solution, functional monomer prepared by preparation example 3 and toughening component prepared by preparation example 6; the modified glass fiber is prepared from the following raw materials by weight parts: 62 parts of silicon dioxide, 18 parts of aluminum oxide, 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 the high-toughness glass fiber comprises the following steps:

[0093] Step S1, mix the raw materials in the modified glass fiber according to the weight parts, melt and draw to prepare the glass fiber blank, wherein, the heating temperature of melting is set to 1300℃, heat preservation for 5h, then increase the temperature to 1500℃ at the rate of 10℃ / min, heat preservation for 11h, the speed of the drawing machine is set to 3m / min;

[0094] Step S2, the glass fiber blank is cooled and shaped by water, then washed by water, the water washing temperature is set to 32℃, then placed in 720℃ for 1.8h, the glass fiber preform is obtained;

[0095] Step S3, the glass fiber preform is placed in the etching solution, then placed in the ultrasonic frequency of 45kHz, ultrasonic power of 600w, ultrasonic oscillation treatment for 36min, then taken out, placed in the modification liquid, control the stirring speed of 650rpm, stirring reaction for 10h, then washed by anhydrous ethanol and deionized water for 5 times, dried at 70℃ to constant weight, the modified glass fiber is obtained, wherein, the mass ratio of glass fiber, etching solution and modification liquid is 1:60:30, the etching solution is mixed by ammonium fluoride, 37% mass fraction hydrochloric acid solution and deionized water according to the mass ratio of 5:3:300, the modification liquid is mixed by anhydrous DMF, KH-550 and deionized water according to the mass ratio of 35:0.2:2;

[0096] Step S4, the modified glass fiber is immersed in the functional solution, then the functional monomer, the toughening component and the benzoin dimethyl ether are added, control the stirring speed of 800rpm, stir for 20min to be uniform, then placed in the ultraviolet light with the wavelength peak of 365nm and the intensity of 80mw / cm 2 , irradiate for 20min, control the irradiation temperature of 65℃, then heat to 95℃, stir for 1.0h, filter, dry, the high-toughness glass fiber is obtained, wherein, 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 mixed by dopamine hydrochloride and Tris-HCl buffer according to the mass ratio of 10:1000, the pH value of Tris-HCl buffer is 8.5.

[0097] Comparative Example 1

[0098] The comparative example provides a high-toughness glass fiber, which comprises modified glass fiber, functional solution, functional monomer prepared by comparative preparation example 1 and toughening component prepared by preparation example 4; the modified glass fiber is prepared from the following raw materials by weight parts: 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.

[0099] The preparation method of the high-toughness glass fiber comprises the following steps:

[0100] Step S1, mix the raw materials in the modified glass fiber according to the weight parts, melt and draw to prepare the glass fiber blank, wherein, the heating temperature of melting is set to 1200℃, heat preservation for 4h, then heat to 1400℃ at the rate of 10℃ / min, heat preservation for 9h, the speed of the drawing machine is set to 2m / min;

[0101] Step S2, the glass fiber blank is cooled and shaped by water, then washed by water, the water washing temperature is set to 28℃, then placed in 660℃ for 1.4h, the glass fiber preform is obtained;

[0102] Step S3, the glass fiber preform is placed in the etching solution, then placed in the ultrasonic frequency of 35kHz and ultrasonic power of 500w, ultrasonic oscillation treatment for 30min, then taken out, placed in the modification solution, control the stirring speed to 550rpm, stirring reaction for 8h, then washed by anhydrous ethanol and deionized water for 3 times, dried at 60℃ to constant weight, the modified glass fiber is obtained, wherein, the mass ratio of glass fiber, etching solution and modification solution is 1:40:20, the etching solution is mixed by ammonium fluoride, 37% mass fraction hydrochloric acid solution and deionized water according to the mass ratio of 5:3:250, the modification solution is mixed by anhydrous DMF, KH-550 and deionized water according to the mass ratio of 35:0.1:2;

[0103] Step S4, the modified glass fiber is immersed in the functional solution, then the functional monomer, the toughening component and the benzoin dimethyl ether are added, control the stirring speed to 700rpm, stir for 12min to be uniform, then placed in the ultraviolet light with the wavelength peak of 365nm and the intensity of 80mw / cm 2 , irradiate for 10min, control the irradiation temperature to 55℃, then heat to 85℃, stir for 0.6h, filter, dry, the high-toughness glass fiber is obtained, wherein, 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 mixed by dopamine hydrochloride and Tris-HCl buffer according to the mass ratio of 2:1000, the pH value of Tris-HCl buffer is 7.5.

[0104] Comparative Example 2

[0105] The comparative example provides a high-toughness glass fiber, which comprises modified glass fiber, functional solution, functional monomer prepared by comparative preparation example 2 and toughening component prepared by preparation example 4; the modified glass fiber is prepared from the following raw materials by weight parts: 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.

[0106] The preparation method of the high-toughness glass fiber comprises the following steps:

[0107] Step S1, mix the raw materials in the modified glass fiber according to the weight parts, melt and draw to prepare the glass fiber blank, wherein, the heating temperature of melting is set to 1200℃, heat preservation for 4h, then heat to 1400℃ at the rate of 10℃ / min, heat preservation for 9h, the speed of the drawing machine is set to 2m / min;

[0108] Step S2, the glass fiber blank is cooled and shaped by water, then washed by water, the water washing temperature is set to 28℃, then placed in 660℃ for 1.4h, the glass fiber preform is obtained;

[0109] Step S3, the glass fiber preform is placed in the etching solution, then placed in the ultrasonic frequency of 35kHz, ultrasonic power of 500w, ultrasonic oscillation treatment for 30min, then taken out, placed in the modification solution, control the stirring speed of 550rpm, stirring reaction for 8h, then washed by anhydrous ethanol and deionized water for 3 times, dried at 60℃ to constant weight, the modified glass fiber is obtained, wherein, the mass ratio of glass fiber, etching solution and modification solution is 1:40:20, the etching solution is mixed by ammonium fluoride, 37% mass fraction hydrochloric acid solution and deionized water according to the mass ratio of 5:3:250, the modification solution is mixed by anhydrous DMF, KH-550 and deionized water according to the mass ratio of 35:0.1:2;

[0110] Step S4, the modified glass fiber is immersed in the functional solution, then the functional monomer, the toughening component and the benzoin dimethyl ether are added, control the stirring speed of 700rpm, stir for 12min to be uniform, then placed in the ultraviolet light with the wavelength peak of 365nm and the intensity of 80mw / cm 2 , irradiate for 10min, control the irradiation temperature of 55℃, then increase the temperature to 85℃, maintain the stirring speed unchanged, continue to stir for 0.6h, filter, dry at 70℃, the high-toughness glass fiber is obtained, wherein, 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 mixed by dopamine hydrochloride and Tris-HCl buffer according to the mass ratio of 2:1000, the pH value of Tris-HCl buffer is 7.5.

[0111] Comparative Example 3

[0112] The comparative example provides a high-toughness glass fiber, which comprises modified glass fiber, functional solution, functional monomer prepared by preparation example 1 and toughening component prepared by comparative preparation example 3; the modified glass fiber is prepared from the following raw materials by weight parts: 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.

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

[0114] Step S1, mix the raw materials in the modified glass fiber according to the weight parts, melt and draw to prepare the glass fiber blank, wherein, the heating temperature of melting is set to 1200℃, heat preservation for 4h, then increase the temperature to 1400℃ at the rate of 10℃ / min, heat preservation for 9h, the speed of the drawing machine is set to 2m / min;

[0115] Step S2, the glass fiber blank is cooled and shaped by water, then washed by water, the water washing temperature is set to 28℃, then placed in 660℃ for 1.4h, the glass fiber preform is obtained;

[0116] Step S3, the glass fiber preform is placed in the etching solution, then placed in the ultrasonic frequency of 35kHz, ultrasonic power of 500w, ultrasonic oscillation treatment for 30min, then taken out, placed in the modification solution, control the stirring speed of 550rpm, stirring reaction for 8h, then washed by anhydrous ethanol and deionized water for 3 times, dried at 60℃ to constant weight, the modified glass fiber is obtained, wherein, the mass ratio of glass fiber, etching solution and modification solution is 1:40:20, the etching solution is mixed by ammonium fluoride, 37% mass fraction hydrochloric acid solution and deionized water according to the mass ratio of 5:3:250, the modification solution is mixed by anhydrous DMF, KH-550 and deionized water according to the mass ratio of 35:0.1:2;

[0117] Step S4, the modified glass fiber is immersed in the functional solution, then the functional monomer, the toughening component and the benzoin dimethyl ether are added, control the stirring speed of 700rpm, stir for 12min to be uniform, then placed in the ultraviolet light with the wavelength peak of 365nm and the intensity of 80mw / cm 2 , irradiate for 10min, control the irradiation temperature of 55℃, then increase the temperature to 85℃, maintain the stirring speed unchanged, continue to stir for 0.6h, filter, dry at 70℃, the high-toughness glass fiber is obtained, wherein, 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 mixed by dopamine hydrochloride and Tris-HCl buffer according to the mass ratio of 2:1000, the pH value of Tris-HCl buffer is 7.5.

[0118] Comparative Example 4

[0119] The comparative example provides a high-toughness glass fiber, which comprises modified glass fiber, functional solution, functional monomer prepared by preparation example 1 and toughening component prepared by comparative preparation example 4; the modified glass fiber is prepared from the following raw materials by weight parts: 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.

[0120] The preparation method of the high-toughness glass fiber comprises the following steps:

[0121] Step S1, mix the raw materials in the modified glass fiber according to the weight parts, melt and draw to prepare the glass fiber blank, wherein, the heating temperature of melting is set to 1200℃, heat preservation for 4h, then increase the temperature to 1400℃ at the rate of 10℃ / min, heat preservation for 9h, the speed of the drawing machine is set to 2m / min;

[0122] Step S2, the glass fiber blank is cooled and shaped by water, then washed by water with a temperature of 28℃, and then treated at 660℃ for 1.4h to obtain a glass fiber preform;

[0123] Step S3, the glass fiber preform is placed in an etching solution, then treated by ultrasonic oscillation at an ultrasonic frequency of 35kHz and an ultrasonic power of 500w for 30min, taken out, then placed in a modification solution and stirred at a speed of 550rpm for 8h, then washed by anhydrous ethanol and deionized water for 3 times in sequence, and dried at 60℃ until constant weight to obtain modified glass fiber, wherein the mass ratio of the glass fiber, the etching solution and the modification solution is 1:40:20, the etching solution is mixed by ammonium fluoride, a 37% mass fraction hydrochloric acid solution and deionized water according to a mass ratio of 5:3:250, and the modification solution is mixed by anhydrous DMF, KH-550 and deionized water according to a mass ratio of 35:0.1:2;

[0124] Step S4, the modified glass fiber is immersed in a functional solution, then a functional monomer, a toughening component and benzoin dimethyl ether are added, and stirred at a speed of 700rpm for 12min until uniform, then irradiated under ultraviolet light with a wavelength peak of 365nm and an intensity of 80mw / cm 2 for 10min, the irradiation temperature is controlled at 55℃, then the temperature is increased to 85℃, the speed is kept unchanged, and the stirring reaction is continued for 0.6h, then filtered and dried at 70℃ to obtain high-toughness glass fiber, wherein 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 mixed by dopamine hydrochloride and Tris-HCl buffer according to a mass ratio of 2:1000, and the pH value of the Tris-HCl buffer is 7.5.

[0125] Performance test

[0126] The glass fibers with a diameter of 5μm obtained in the above examples 1-3 and comparative examples 1-4 are tested for tensile strength according to the standard ASTM D3039 / D3039M, and the glass fibers in the above examples 1-5 and comparative examples 1-4 are woven into fabrics on a loom, and the friction and wear properties of the materials are evaluated on a MM-200 type friction and wear tester according to GB3960-83, and the test results are shown in Table 1:

[0127] Table 1 Test of toughness and wear resistance of the glass fibers prepared in examples 1-3 and comparative examples 1-4

[0128]

[0129] As shown in Table 1, compared with comparative example 1-4, the high-toughness glass fiber prepared in example 1-3 has more excellent toughness and wear resistance.

[0130] The embodiments are only illustrative of the present application, and are not intended to limit the present application, and those skilled in the art can make modifications to the embodiments without creative contribution after reading the specification, but as long as the modifications 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 by, Preparation method of modified glass fiber Step S1, by weight parts, the raw materials in the modified glass fiber are mixed, and the glass fiber is prepared by melting and drawing; Step S2, the glass fiber blank is cooled and formed, then washed with water, and then heat treated to obtain a glass fiber preform; Step S3, the glass fiber preform is placed in an etching solution, treated by ultrasonic oscillation, taken out, then placed in a modification solution, stirred and reacted for 8-10h, washed and dried to obtain the modified glass fiber; Step S4, the modified glass fiber is immersed in a functional solution, then functional monomers, toughening components and benzoin dimethyl ether are added, stirred uniformly, irradiated by ultraviolet light for 10-20min, the irradiation temperature is controlled at 55-65℃, then heated to 85-95℃, stirred and reacted for 0.6-1.0h, filtered and dried to obtain the high-toughness glass fiber; The modified glass fiber is prepared from the following raw materials 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 solution at a mass ratio of 2-10:1000; The functional monomer is prepared by the following steps: first, the modified nano-titanium dioxide is prepared by hydrolysis of titanium chloride under the dispersion of dodecyl dimethyl hydroxy propyl sulfobetaine, then the core-shell particles are prepared by hydrolysis coating of tetraethyl orthosilicate, then the amino core-shell particles are prepared by modification of KH-550, and finally the disulfide monomer is prepared by amidation reaction of the amino core-shell particles with 3,3'-dithiodipropionic acid, and then the disulfide monomer is prepared by ring-opening esterification reaction with allyl glycidyl ether; The toughening component is prepared by the following steps: first, the epoxidized ethylene-propylene-diene rubber is prepared by oxidation of ethylene-propylene-diene rubber with formic acid and hydrogen peroxide, and then the toughening component is prepared by ring-opening esterification reaction of the epoxidized ethylene-propylene-diene rubber with 4-mercaptopyridine dicarboxylic acid.

2. A high-tenacity glass fiber as defined in claim 1, wherein, The functional monomer is prepared by the following steps: Step A1, titanium chloride and deionized water are added to anhydrous ethanol, stirred uniformly, heated to 35-45℃, dodecyl dimethyl hydroxy propyl sulfobetaine is added while stirring, then heated to 112-124℃, stirred and reacted for 6-8h, after the reaction is completed, cooled to room temperature, centrifuged, washed and dried to obtain the modified nano-titanium dioxide, then the modified nano-titanium dioxide is added to cyclohexane, stirred until uniform, the pH value is adjusted to 8.6-9.2, tetraethyl orthosilicate is added, heated to 58-64℃, and continued to stir for 5-8h, after the reaction is completed, the pH value is adjusted to neutral, centrifuged, washed and dried to obtain the core-shell particles; Step A2, the core-shell particles, deionized water, anhydrous ethanol and KH-550 are ultrasonically mixed uniformly, heated to 48-56℃, and continued to stir for 5.2-5.8h, centrifuged, washed and dried to obtain the aminated core-shell particles, the aminated core-shell particles are added to anhydrous DMF, stirred uniformly, and the mixed solution a of N,N-dicyclohexyl carbodiimide, 4-dimethylamino pyridine, 3,3'-dithiodipropionic acid and anhydrous DMF is added dropwise, after the dropwise addition is completed, heated to 78-82℃, stirred and reacted for 2.4-2.8h, after the reaction is completed, centrifuged, washed and dried to obtain the disulfide monomer; Step A3, the dithio monomer is added into anhydrous DMF, warmed to 45-55℃, stirred evenly, adjusted to pH 9-10, dropwise added mixed solution b of allyl glycidyl ether and isopropyl alcohol, control in 30min drop, drop, warmed to 76-82℃, continue to stir for 8-12h, adjust the pH to neutral, rotary evaporation, washing and drying, to get functional monomer.

3. A high-tenacity glass fiber as claimed in claim 2, wherein, In the step A1, the mass ratio of titanium chloride, deionized water, anhydrous ethanol and dodecyl dimethyl hydroxy propyl 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-tenacity glass fiber as claimed in claim 2, wherein, In the step A2, the mass ratio of core-shell particles, deionized water, anhydrous ethanol and KH-550 is 2.4-3.2: 11-13: 22-30: 0.16-0.30, and the mass ratio of amino core-shell particles, anhydrous DMF and mixed solution a is 2.2: 40-50: 16, and in the mixed solution a, the mass ratio of N, N-dicyclohexyl carbodiimide, 4-dimethyl amino pyridine, 3, 3'-dithiodipropionic acid and anhydrous DMF is 0.40-0.48: 0.20-0.24: 0.36-0.44:

10.

5. A high-tenacity glass fiber as claimed in claim 2, wherein, In the step A3, the mass ratio of dithio monomer, anhydrous DMF and mixed solution b is 2-4: 36-42: 15-25.

6. A high-tenacity glass fiber as claimed in claim 5, wherein, In the mixed solution b, the mass ratio of allyl glycidyl ether and isopropyl alcohol is 1.2-1.6: 12-22.

7. A high-tenacity glass fiber as claimed in claim 1, wherein, The toughening component is prepared by the following steps: Step B1, the ternary ethylene propylene rubber is added into n-hexane, stirred and dissolved, warmed to 45-55℃, then formic acid and Tween-80 are added, stirred evenly, dropwise added hydrogen peroxide, control in 30min drop, drop, stirred for 8-10h, after the reaction is completed, the sodium carbonate aqueous solution is added again, continue to stir for 10-12min, stand for 15-25min, washing, then added into anhydrous ethanol, flocculation and precipitation for 2-3h, drying, to get epoxidized ternary ethylene propylene rubber; Step B2, the epoxy ternary ethylene propylene rubber is added into toluene, stirred evenly, warmed to 65-75℃, dropwise added mixed solution c of tetrabutylammonium bromide, 4-mercaptopyridine dicarboxylic acid and anhydrous DMF, control in 15min drop, drop, continue to stir for 6-8h, centrifugation, the precipitate is washed and dried, to get toughening component.

8. A high-tenacity glass fiber as claimed in claim 7, wherein, In the step B1, the mass ratio of ternary ethylene propylene 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 sodium carbonate aqueous solution is 0.04-0.08%.

9. A high-tenacity glass fiber as claimed in claim 7, wherein, In step B2, the mass ratio of the epoxy group-containing EPDM, toluene and the mixed solution c is 18-22:240-260:52-64, and 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.

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