CN115044173B - Corrosion-resistant high-elasticity composite fiber and preparation method thereof - Google Patents
Corrosion-resistant high-elasticity composite fiber and preparation method thereof Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a corrosion-resistant high-elasticity composite fiber and a preparation method thereof. The pre-impregnation liquid is resin pre-impregnation liquid, and the dendritic nano silicon dioxide is added into the resin pre-impregnation liquid, so that the resin pre-impregnation liquid can be used as a reinforcing filler, can also combine glass fibers and resin to play a role of a bridge, ensures good interface combination between the glass fibers and the resin, reduces or even avoids the influence on the mechanical property of the material caused by the internal defects of the base material such as base material cavities and resin cavities caused by poor impregnation, and prolongs the service life of the corrosion-resistant high-elasticity composite fiber.
Description
Technical Field
The invention relates to the technical field of glass fiber composite materials, in particular to a corrosion-resistant high-elasticity composite fiber and a preparation method thereof.
Background
The composite material is a solid material consisting of two or more independent phases, and is prepared by mutually making up for deficiencies and optimally combining several materials based on the characteristics of different materials and different forming processes, so that the composite material has the excellent characteristics of the several materials.
Glass fiber is an inorganic non-metallic material with excellent performance and a wide variety of types, is fibrous glass, and is prepared by the procedures of high-temperature melting, wire drawing, winding, weaving and the like. Glass fibers are commonly used as reinforcing materials in composite materials, and a glass fiber resin-based composite material is the most widely used composite material and the most mature process at present, and has a plurality of excellent properties: the glass fiber resin-based composite material has the characteristics of easy acquisition, low elongation at break, high elastic modulus, fire resistance, mildew resistance, light weight, strong acid and alkali corrosion resistance, flexible designability, excellent manufacturing process and other properties such as electric insulation property, good thermal property and the like, the excellent properties enable the application of the glass fiber resin-based composite material in the fields of military aviation, mechanical manufacturing, civil engineering and the like to have a history of nearly forty years, the glass fiber resin-based composite material also has wide application in a plurality of fields such as automobile manufacturing, electrical chemical industry, electronic products, life, leisure and entertainment and the like, and the composite material replaces some traditional materials such as metal, alloy, ceramic or wood products and the like in a plurality of application occasions.
Corrosion is a major worldwide problem, and materials applied in various fields inevitably come into contact with various corrosive media, so that it is very necessary to improve the corrosion resistance of the materials.
CN104369475A discloses a corrosion-resistant glass fiber cloth, which comprises a resin material layer at the uppermost layer, a curing agent at the middle layer and a glass fiber layer at the lowermost layer, wherein the resin material layer is polycarbonate, the glass fiber layer is glass fiber, the polycarbonate accounts for 23% -44% of the total weight of the corrosion-resistant glass fiber cloth, the curing agent accounts for 10% -24% of the total weight of the corrosion-resistant glass fiber cloth, and the glass fiber accounts for 44% -55% of the total weight of the corrosion-resistant glass fiber cloth. The corrosion-resistant glass fiber cloth provided by the invention has the advantages of good insulation, strong heat resistance, good corrosion resistance and high mechanical strength. However, the present invention has a problem that the resin material layer and the glass fiber layer have poor affinity and insufficient bonding strength, and the composite material has insufficient strength and is easily broken.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a durable corrosion-resistant composite glass fiber material.
In order to achieve the purpose, the invention provides the corrosion-resistant high-elasticity composite fiber, the preparation of the corrosion-resistant high-elasticity composite fiber material is completed through the processes of pre-dipping, laminating, mould pressing, curing and the like of the glass fiber cloth, the bonding capacity of the glass fiber and a resin material is improved, and the interlayer bonding force of the glass fiber cloth is improved; the prepreg glass fiber cloth is laminated, so that the defects of large brittleness, poor elasticity and low durability of single-layer glass fiber are overcome, and the subversive increase of the performance of the glass fiber composite material is realized.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of corrosion-resistant high-elasticity composite fiber comprises the following steps:
and soaking the glass fiber cloth in the resin pre-soaking solution, taking out, laminating, compression molding and post-curing to obtain the corrosion-resistant high-elasticity composite fiber.
Preferably, the preparation method of the corrosion-resistant high-elasticity composite fiber comprises the following steps:
s1, soaking glass fiber cloth in a resin pre-soaking solution for 20-24h; taking out after the infiltration is finished, and airing for later use;
s2, laminating the soaked glass fiber cloth, and totally laminating 20-100 layers;
s3, performing die pressing on the laminated glass fiber cloth by using a flat machine to obtain a glass fiber composite material subjected to die pressing forming, wherein the die pressing forming temperature is 110-180 ℃, and the forming pressure is 5-220kg/cm 2 Vacuumizing for 0-30 seconds, exhausting for 0-100 times, and molding for 1-60 minutes;
s4, taking out the glass fiber composite material subjected to compression molding, molding a product by using a mold, and finally performing post-curing treatment, wherein the post-curing temperature is 110-180 ℃, and the post-curing time is 1-60 minutes, so that the corrosion-resistant high-elasticity composite fiber is obtained.
Preferably, the glass fiber cloth is one of alkali-free glass fiber cloth, high-strength glass fiber cloth and high-modulus glass fiber cloth.
Preferably, the resin pre-impregnation liquid comprises the following components in parts by weight: 20-80 parts of epoxy vinyl ester resin, 5-30 parts of reinforcing filler, 10-40 parts of curing agent, 0.1-1 part of accelerator, 1-5 parts of antioxidant and 100-150 parts of solvent.
The inventor adopts epoxy vinyl ester resin as a film forming agent, the epoxy vinyl ester resin is a deformed epoxy resin formed by ring-opening polymerization reaction of epoxy resin and acrylic acid or methacrylic acid, is a resin with excellent corrosion resistance, has the characteristics of low density, excellent corrosion resistance, processability and the like, and is widely applied to glass fiber reinforced plastic containers, pipelines and chemical anticorrosion engineering.
Preferably, the dosage ratio of the glass fiber cloth to the resin pre-impregnation liquid is 1.
Preferably, the reinforcing filler is one or a mixture of more than two of montmorillonite, calcium carbonate, diatomite, nano silica, boron nitride, vermiculite, magnesium oxide and alumina;
preferably, the reinforcing filler is nano silica; further preferably, the reinforcing filler is dendritic nano silica, and the preparation method thereof is as follows:
(1) Dissolving urea and hexadecyl trimethyl ammonium bromide in water; adding cyclohexane and isopropanol and stirring; adding tetraethyl orthosilicate and heating for reaction; centrifuging and collecting precipitate; washing and drying the precipitate to obtain fibrous nano silicon dioxide;
(2) Dispersing fibrous nano silicon dioxide in toluene; adding 3-aminopropyltriethoxysilane, and heating for reaction; cooling, centrifuging and collecting precipitate; washing and drying the precipitate to obtain aminopropyl functionalized fibrous nano silicon dioxide;
(3) Dispersing aminopropyl functionalized fibrous nano silicon dioxide and methyl acrylate in methanol water solution for reaction; filtering and collecting a filter cake, and washing and drying the filter cake to obtain ester group functionalized fibrous nano silicon dioxide; and then adding the ester group functionalized fibrous nano-silica into triethylamine for reaction, filtering, and washing and drying a filter cake to obtain the dendritic nano-silica.
Further preferably, the preparation method of the dendritic nano silica comprises the following steps:
(1) Dissolving 2-4g of urea and 3-5g of hexadecyl trimethyl ammonium bromide in 20-50mL of water at room temperature; adding 100-150mL of cyclohexane and 1-5mL of isopropanol, and stirring at the rotating speed of 800-1000rpm for 2-3h; then 8-15mL of tetraethyl orthosilicate is dripped at the speed of 1-2 drops/second; after the dropwise addition is finished, heating to 60-80 ℃, and reacting for 20-24h; after the reaction is finished, centrifuging the reaction solution for 10-20min, and collecting white precipitate; washing the precipitate with water and 75-99wt% ethanol water solution for 2-3 times, and drying at 40-60 deg.C for 10-12 hr to obtain fibrous nanometer silicon dioxide;
(2) Dispersing 1-3g of fibrous nano silicon dioxide in 50-100mL of toluene in the nitrogen atmosphere; adding 1-5mL of 3-aminopropyltriethoxysilane; heating to 100-120 deg.C, and reacting for 10-12h; cooling to room temperature after the reaction is finished, centrifuging for 10-20min, and collecting precipitate; washing the precipitate with 75-99wt% ethanol water solution for 2-3 times, and drying at 50-80 deg.C for 20-24 hr to obtain aminopropyl functionalized fibrous nanometer silicon dioxide;
(3) Dispersing 2-4g of aminopropyl functionalized fibrous nano silicon dioxide and 3-5g of methyl acrylate in 150-250mL of 75-99wt% methanol aqueous solution at room temperature for reaction for 10-12h; filtering and collecting a filter cake, washing the filter cake for 2-3 times by using 75-99wt% methanol water solution, and drying at 50-80 ℃ for 8-10h to obtain ester group functionalized fibrous nano silicon dioxide; and then adding ester group functionalized fibrous nano-silica into 100-200mL triethylamine, reacting for 5-8h at 50-80 ℃, filtering after the reaction is finished, washing a filter cake for 2-3 times by using water, and drying for 8-10h at 50-80 ℃ to obtain the dendritic nano-silica.
Although the epoxy vinyl ester resin has strong adhesiveness, the epoxy vinyl ester resin has high crosslinking density during curing, great brittleness, poorer fatigue resistance and impact toughness, and particularly poor heat resistance and peeling strength, thereby influencing the adhesive force and the corrosion resistance of an epoxy film layer; therefore, the inventor adds the nano-silica in the formula of the pre-immersion liquid for toughening, but the nano-silica is easy to agglomerate in a resin matrix and cannot be well dispersed, so that the particle size is increased, and the stability of the pre-immersion liquid is influenced.
Because the glass fiber is an inorganic material and the resin matrix is an organic material, the affinity of the glass fiber with the inorganic surface is poor, the bonding strength is not enough, and the composite material is not strong enough and is easy to damage. The inventor adds the dendritic nano-silica particles which can be used as a reinforcing filler and can also combine the glass fiber with the resin to play a role of a bridge, the dendritic nano-silica particles are uniformly coated on the surface of the fiber to fill the original micro-cracks and gullies on the surface of the glass fiber protofilament, the surface roughness of the glass fiber is increased, the contact area between the glass fiber and a resin matrix is increased, the mechanical anchoring of the glass fiber and the resin is strengthened, good interface combination between the glass fiber and the resin is ensured, the influence on the mechanical property of the material caused by the internal defects of the substrate such as substrate cavities, resin cavities and the like caused by poor impregnation is reduced or even eliminated, and the service life and the durability of the corrosion-resistant high-elasticity composite fiber are improved.
Preferably, the curing agent is one or a mixture of more than two of isophorone diamine, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, 1,2-diaminocyclohexane and 4,4-diaminodiphenyl sulfone.
Preferably, the accelerator is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole, N-dimethylbenzylamine, boron trifluoride ethylamine, triethylamine, hexamethyltetramine, cobalt naphthenate and cobalt isooctanoate.
Preferably, the antioxidant is one or a mixture of more than two of hindered phenol antioxidant, phosphite antioxidant and aromatic amine antioxidant.
Preferably, the solvent is one or a mixture of more than two of toluene, acetone, butanone, ethylene glycol dimethyl ether, N-dimethylformamide and ethanol.
Compared with the prior art, the invention has the following beneficial effects: (1) The composite fiber prepared by the invention has excellent electrical insulation performance, corrosion resistance, strong heat resistance, environmental protection, no pollution, good toughness, good impact resistance and long service life; (2) According to the invention, the dendritic nano-silica is added, so that the flexibility of the epoxy resin is improved, and the adhesive force and the corrosion resistance of the epoxy film layer are further improved; meanwhile, the surface wettability of the glass fiber cloth and the resin is improved, good interface combination between the glass fiber cloth and the resin is ensured, the influence on the mechanical property of the composite material caused by the internal defects of the base material such as base material cavities and resin cavities caused by poor impregnation is reduced or even eliminated, and the service life of the corrosion-resistant high-elasticity composite fiber is prolonged.
Detailed Description
For the sake of brevity, the articles used in the following examples are all commercially available products unless otherwise specified, and the methods used are conventional methods unless otherwise specified.
The invention uses part of raw materials with the following sources:
the alkali-free glass fiber cloth has the elongation at break of 19 percent and the thickness of 0.4mm, and is made by Hebeixin environmental protection science and technology Limited.
Epoxy vinyl ester resin with the total solid content of more than or equal to 85 percent and the surface drying time of 2 hours, gallery Qiao Sha anticorrosive materials Limited.
The nanometer silicon dioxide has the mesh number of 1200 meshes, the hardness of 90, the whiteness of 90 and the content of 90 percent, and is a new material for Zhonghang (Shandong) Co.
1,2-diaminocyclohexane, purity 99%, relative density 1g/cm 3 The boiling point was 193.6 ℃ and the flash point was 75 ℃ and the product of technical health (Hubei) Co.
Cobalt naphthenate with content not less than 8%, density of 0.921g/mL, specific gravity of 0.95, flash point of 120F, and environment-friendly science and technology Limited of Wandebeng, jinan.
Tris (nonylphenyl) phosphite, CAS number 26523-78-4, acid number <0.05, phosphorus content >4%, gukubei shi shui biotechnology limited.
Example 1
A preparation method of corrosion-resistant high-elasticity composite fiber comprises the following steps:
s1, uniformly mixing 300g of epoxy vinyl ester resin, 100g of dendritic nano-silica, 200g1, 2-diaminocyclohexane, 80g of cobalt naphthenate, 30g of tris (nonylphenyl) phosphite and 1000g of acetone to obtain a resin pre-impregnation solution; then soaking 25g of alkali-free glass fiber cloth in the resin pre-soaking liquid for 24h; taking out after the infiltration is finished, and airing for later use;
s2, laminating the soaked alkali-free glass fiber cloth at an angle of 30 degrees, and totally laminating 30 layers;
s3, carrying out die pressing on the laminated alkali-free glass fiber cloth by using a flat machine to obtain a glass fiber composite material subjected to die pressing forming, wherein the die pressing forming temperature is 150 ℃, and the forming pressure is 150kg/cm 2 Vacuumizing for 25 seconds, exhausting for 20 times, and molding for 15 minutes;
s4, taking out the glass fiber composite material subjected to compression molding, molding the product by using a mold, and finally performing post-curing treatment, wherein the post-curing temperature is 165 ℃, and the post-curing time is 30 minutes to obtain the corrosion-resistant high-elasticity composite fiber.
The preparation method of the dendritic nano silicon dioxide comprises the following steps:
(1) At room temperature, 3.5g of urea and 4.8g of hexadecyl trimethyl ammonium bromide are dissolved in 30mL of water; adding 120mL of cyclohexane and 5mL of isopropanol, and stirring for 2h at the rotating speed of 1000 rpm; then, 10mL of tetraethyl orthosilicate is dripped at the speed of 1 drop/second; after the dropwise addition, heating to 60 ℃ and reacting for 24 hours; after the reaction is finished, centrifuging the reaction solution for 15min, and collecting white precipitate; washing the precipitate with water and 99wt% ethanol water solution for 3 times, and drying at 60 deg.C for 12 hr to obtain fibrous nanometer silica;
(2) Dispersing 2.5g of fibrous nano silicon dioxide in 80mL of toluene under the nitrogen atmosphere; adding 5mL of 3-aminopropyltriethoxysilane; heating to 110 ℃, and reacting for 12h; cooling to room temperature after the reaction is finished, centrifuging for 10min, and collecting precipitate; washing the precipitate with 99wt% ethanol water solution for 3 times, and drying at 80 deg.C for 24 hr to obtain aminopropyl functionalized fibrous nanometer silica;
(3) Dispersing 2.5g of aminopropyl functionalized fibrous nano silicon dioxide and 4.6g of methyl acrylate in 200mL of 99wt% methanol aqueous solution at room temperature for reaction for 12h; filtering and collecting a filter cake, washing the filter cake for 3 times by using a 99wt% methanol aqueous solution, and drying at 60 ℃ for 10 hours to obtain ester group functionalized fibrous nano-silica; and then adding ester group functionalized fibrous nano-silica into 150mL of triethylamine, reacting for 6h at 60 ℃, filtering after the reaction is finished, washing a filter cake for 3 times by using water, and drying for 10h at 60 ℃ to obtain the dendritic nano-silica.
Example 2
A preparation method of corrosion-resistant high-elasticity composite fibers comprises the following steps:
s1, uniformly mixing 300g of epoxy vinyl ester resin, 100g of nano silicon dioxide, 200g of 1, 2-diaminocyclohexane, 80g of cobalt naphthenate, 30g of tris (nonylphenyl) phosphite ester and 1000g of acetone to obtain a resin pre-impregnation solution; then soaking 25g of alkali-free glass fiber cloth in the resin pre-soaking liquid for 24h; taking out after the soaking is finished, and airing for later use;
s2, laminating the soaked alkali-free glass fiber cloth at an angle of 30 degrees, and totally laminating 30 layers;
s3, carrying out die pressing on the laminated alkali-free glass fiber cloth by using a flat machine to obtain a glass fiber composite material subjected to die pressing forming, wherein the die pressing forming temperature is 150 ℃, and the forming pressure is 150kg/cm 2 Vacuumizing for 25 seconds, exhausting for 20 times, and molding for 15 minutes;
s4, taking out the glass fiber composite material subjected to compression molding, molding the product by using a mold, and finally performing post-curing treatment, wherein the post-curing temperature is 165 ℃, and the post-curing time is 30 minutes to obtain the corrosion-resistant high-elasticity composite fiber.
Comparative example 1
A preparation method of corrosion-resistant high-elasticity composite fiber comprises the following steps:
s1, uniformly mixing 300g of epoxy vinyl ester resin, 100g of fibrous nano silicon dioxide, 200g1, 2-diaminocyclohexane, 80g of cobalt naphthenate, 30g of tris (nonylphenyl) phosphite ester and 1000g of acetone to obtain a resin pre-impregnation solution; then soaking 25g of alkali-free glass fiber cloth in the resin pre-soaking liquid for 24h; taking out after the infiltration is finished, and airing for later use;
s2, laminating the soaked alkali-free glass fiber cloth at an angle of 30 degrees, and totally laminating 30 layers;
s3, carrying out die pressing on the laminated alkali-free glass fiber cloth by using a flat machine to obtain a glass fiber composite material subjected to die pressing forming, wherein the die pressing forming temperature is 150 ℃, and the forming pressure is 150kg/cm 2 Vacuumizing for 25 seconds, exhausting for 20 times, and molding for 15 minutes;
s4, taking out the glass fiber composite material subjected to compression molding, molding the product by using a mold, and finally performing post-curing treatment, wherein the post-curing temperature is 165 ℃, and the post-curing time is 30 minutes to obtain the corrosion-resistant high-elasticity composite fiber.
The preparation method of the fibrous nano silicon dioxide comprises the following steps:
3.5g of urea and 4.8g of cetyltrimethylammonium bromide were dissolved in 30mL of water at room temperature; adding 120mL of cyclohexane and 5mL of isopropanol, and stirring for 2h at the rotating speed of 1000 rpm; then, 10mL of tetraethyl orthosilicate is dripped at the speed of 1 drop/second; after the dropwise addition, heating to 60 ℃ and reacting for 24 hours; after the reaction is finished, centrifuging the reaction solution for 15min, and collecting white precipitate; the precipitate was washed 3 times with water and 99wt% ethanol aqueous solution, respectively, and then dried at 60 ℃ for 12 hours to obtain fibrous nano-silica.
Comparative example 2
A preparation method of corrosion-resistant high-elasticity composite fiber comprises the following steps:
s1, uniformly mixing 300g of epoxy vinyl ester resin, 100g of aminopropyl functionalized fibrous nano silicon dioxide, 200g of 1, 2-diaminocyclohexane, 80g of cobalt naphthenate, 30g of tris (nonylphenyl) phosphite ester and 1000g of acetone to obtain a resin pre-impregnation solution; then soaking 25g of alkali-free glass fiber cloth in the resin pre-soaking liquid for 24h; taking out after the infiltration is finished, and airing for later use;
s2, laminating the soaked alkali-free glass fiber cloth at an angle of 30 degrees, and totally laminating 30 layers;
s3, carrying out die pressing on the laminated alkali-free glass fiber cloth by using a flat machine to obtain a glass fiber composite material subjected to die pressing forming, wherein the die pressing forming temperature is 150 ℃, and the forming pressure is 150kg/cm 2 Vacuumizing for 25 seconds, exhausting for 20 times, and molding for 15 minutes;
s4, taking out the glass fiber composite material subjected to compression molding, molding the product by using a mold, and finally performing post-curing treatment, wherein the post-curing temperature is 165 ℃, and the post-curing time is 30 minutes to obtain the corrosion-resistant high-elasticity composite fiber.
The preparation method of the aminopropyl functionalized fibrous nano silicon dioxide comprises the following steps:
(1) At room temperature, 3.5g of urea and 4.8g of hexadecyl trimethyl ammonium bromide are dissolved in 30mL of water; adding 120mL of cyclohexane and 5mL of isopropanol, and stirring for 2 hours at the rotating speed of 1000 rpm; then, 10mL of tetraethyl orthosilicate is dripped at the speed of 1 drop/second; after the dropwise addition, heating to 60 ℃ and reacting for 24 hours; after the reaction is finished, centrifuging the reaction solution for 15min, and collecting white precipitate; washing the precipitate with water and 99wt% ethanol water solution for 3 times, and drying at 60 deg.C for 12 hr to obtain fibrous nanometer silica;
(2) Dispersing 2.5g of fibrous nano-silica in 80mL of toluene under the nitrogen atmosphere; adding 5mL of 3-aminopropyltriethoxysilane; heating to 110 ℃, and reacting for 12h; cooling to room temperature after the reaction is finished, centrifuging for 10min, and collecting precipitate; washing the precipitate with 99wt% ethanol water solution for 3 times, and drying at 80 deg.C for 24 hr to obtain aminopropyl functionalized fibrous nanometer silica.
Test example 1
And (3) corrosion resistance testing: 0.5g of each of the corrosion-resistant highly elastic composite fibers obtained in examples 1 to 2 and comparative examples 1 to 2 was dried in an oven at 100 ℃ for 1 hour, taken out, placed in a desiccator for cooling, and weighed with an analytical balance to give a mass m 0 Preparing 10wt% sodium oxy-oxide aqueous solution, and respectively putting the weighed composite materials into the sodium oxy-oxide aqueous solution with the concentration to boil for 2 hours; taking out, washing with distilled water, drying in an oven at 105 deg.C for 1 hr, cooling in a desiccator to room temperature, weighing as m 1 Comparing the mass loss rate before and after corrosion, and calculating by the method of (m) 0 -m 1 )/m 0 Each sample was tested 3 times, the test results were averaged and are shown in table 1:
table 1: corrosion resistance test result of corrosion-resistant high-elasticity composite fiber
| Mass loss rate (%) | |
| Example 1 | 0.4 |
| Example 2 | 1.3 |
| Comparative example 1 | 0.9 |
| Comparative example 2 | 0.8 |
As can be seen from the experimental data in table 1, the corrosion-resistant high-elastic composite fiber prepared in example 1 has the best corrosion resistance, and example 1 is different from other examples and comparative examples in that dendritic nano-silica is added, which may be caused by the reason that dendritic nano-silica and epoxy resin form chemical bonds to adhere to the continuous phase of epoxy resin, thereby improving the flexibility of the resin, improving the adhesion of the epoxy film layer, and further improving the corrosion resistance of the material.
Test example 2
And (3) testing the bending strength: the test method is GB/T1449-2005 (test method for bending property of fiber reinforced plastics) test the bending strength of the corrosion-resistant high-elasticity composite fiber prepared in the examples 1-2 and the comparative examples 1-2, a WDW-30 type universal tester is used for adopting an unconstrained support, a sample is broken at a constant loading rate through three-point bending, the test speed is 10mm/min, and the bending strength value is calculated according to the following formula: tau is f ＝(3P b ×l)/(2b×h 2 )
τ f Bending strength, MPa; p b The maximum load when the sample is damaged, N; l is span, mm; b is the width of the sample, mm; h is the specimen height, mm.
Each sample was tested 3 times and the test results averaged and are shown in table 2:
TABLE 2 mechanical property test results of corrosion-resistant high-elastic composite fiber
| Flexural Strength (τ) f ，MPa) | |
| Example 1 | 268 |
| Example 2 | 206 |
| Comparative example 1 | 234 |
| Comparative example 2 | 243 |
As can be seen from the experimental results in table 2, the corrosion-resistant high-elasticity composite fiber prepared in example 1 also has the best mechanical properties, and the probable reason is that the dendritic nano-silica particles can be used as a reinforcing filler, and also can combine the glass fiber with the resin to play a role of a bridge, and the dendritic nano-silica particles are uniformly coated on the surface of the fiber to fill the original micro-cracks and gullies on the surface of the glass fiber strand, thereby increasing the surface roughness of the glass fiber, increasing the contact area between the glass fiber and the resin matrix, strengthening the mechanical anchoring of the glass fiber and the resin, and improving the mechanical properties of the corrosion-resistant high-elasticity composite fiber.
Claims (4)
1. The preparation method of the corrosion-resistant high-elasticity composite fiber is characterized by comprising the following steps of:
s1, soaking glass fiber cloth in a resin pre-soaking solution for 20-24h; taking out after the infiltration is finished, and airing for later use;
s2, laminating the soaked glass fiber cloth, and totally laminating 20-100 layers;
s3, carrying out compression molding on the laminated glass fiber cloth to obtain a glass fiber composite material, wherein the compression molding temperature is 110-180 ℃, the molding pressure is 5-220kg/cm < 2 >, the vacuumizing time is 0-30 seconds, the exhausting frequency is 0-100 times, and the molding time is 1-60 minutes;
s4, taking out the glass fiber composite material subjected to compression molding, molding the product by using a mold, and finally performing post-curing treatment, wherein the post-curing temperature is 110-180 ℃, and the post-curing time is 1-60 minutes to obtain the corrosion-resistant high-elasticity composite fiber;
the resin pre-immersion liquid comprises the following components in parts by weight: 20-80 parts of epoxy vinyl ester resin, 5-30 parts of reinforcing filler, 10-40 parts of curing agent, 0.1-1 part of accelerator, 1-5 parts of antioxidant and 100-150 parts of solvent;
the reinforcing filler is dendritic nano silicon dioxide, and the preparation method comprises the following steps:
(1) Dissolving 2-4g of urea and 3-5g of hexadecyl trimethyl ammonium bromide in 20-50mL of water at room temperature; adding 100-150mL of cyclohexane and 1-5mL of isopropanol, and stirring at the rotating speed of 800-1000rpm for 2-3h; then 8-15mL of tetraethyl orthosilicate is dripped at the speed of 1-2 drops/second; after the dropwise addition is finished, heating to 60-80 ℃, and reacting for 20-24h; after the reaction is finished, centrifuging the reaction solution for 10-20min, and collecting white precipitate; washing the precipitate with water and 75-99wt% ethanol water solution for 2-3 times, and drying at 40-60 deg.C for 10-12 hr to obtain fibrous nanometer silicon dioxide;
(2) Under the atmosphere of nitrogen, 1-3g of fibrous nano silicon dioxide is dispersed in 50-100mL of toluene; adding 1-5mL of 3-aminopropyltriethoxysilane; heating to 100-120 ℃, and reacting for 10-12h; cooling to room temperature after the reaction is finished, centrifuging for 10-20min, and collecting precipitate; washing the precipitate with 75-99wt% ethanol water solution for 2-3 times, and drying at 50-80 deg.C for 20-24 hr to obtain aminopropyl functionalized fibrous nanometer silicon dioxide;
(3) Dispersing 2-4g of aminopropyl functionalized fibrous nano silicon dioxide and 3-5g of methyl acrylate in 150-250mL of 75-99wt% methanol aqueous solution at room temperature for reaction for 10-12h; filtering and collecting a filter cake, washing the filter cake for 2-3 times by using 75-99wt% methanol water solution, and drying at 50-80 ℃ for 8-10h to obtain ester group functionalized fibrous nano silicon dioxide; and then adding ester group functionalized fibrous nano-silica into 100-200mL triethylamine, reacting for 5-8h at 50-80 ℃, filtering after the reaction is finished, washing a filter cake for 2-3 times by using water, and drying for 8-10h at 50-80 ℃ to obtain the dendritic nano-silica.
2. The method for preparing the corrosion-resistant high-elastic composite fiber according to claim 1, wherein the method comprises the following steps: the glass fiber cloth is one of alkali-free glass fiber cloth, high-strength glass fiber cloth and high-modulus glass fiber cloth.
3. The method for preparing the corrosion-resistant high-elastic composite fiber according to claim 1, wherein the method comprises the following steps: the accelerant is one or a mixture of more than two of 2-methylimidazole, 2-ethyl-4-methylimidazole, N-dimethylbenzylamine, boron trifluoride ethylamine, triethylamine, hexamethyltetramine, cobalt naphthenate, cobalt naphthanate and cobalt isooctanoate.
4. The corrosion-resistant high-elasticity composite fiber is characterized in that: the corrosion-resistant high-elasticity composite fiber is prepared by the preparation method of the corrosion-resistant high-elasticity composite fiber according to any one of claims 1 to 3.
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