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CN117487324B - Basalt fiber reinforced corrosion-resistant composite rib and preparation method thereof - Google Patents

Basalt fiber reinforced corrosion-resistant composite rib and preparation method thereof Download PDF

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Publication number
CN117487324B
CN117487324B CN202311591474.3A CN202311591474A CN117487324B CN 117487324 B CN117487324 B CN 117487324B CN 202311591474 A CN202311591474 A CN 202311591474A CN 117487324 B CN117487324 B CN 117487324B
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basalt fiber
parts
fiber reinforced
coupling agent
resistant composite
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CN117487324A (en
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徐强
张增飞
黄胜军
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Zhejiang Xinshuo New Material Co ltd
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Zhejiang Xinshuo New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C08J2475/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/159—Heterocyclic compounds having oxygen in the ring having more than two oxygen atoms in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds

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Abstract

The invention discloses a basalt fiber reinforced anti-corrosion composite bar and a preparation method thereof, which relate to the technical field of composite materials and comprise the following raw materials in parts by weight: 15-25 parts of resin matrix, 75-85 parts of basalt fiber, 4-8 parts of curing agent, 3-5 parts of coupling agent and 4-6 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1 (1-3): 0.8-1.2): 0.4. The composite rib has good corrosion resistance, good mechanical property, excellent ageing resistance and long service life.

Description

Basalt fiber reinforced corrosion-resistant composite rib and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a basalt fiber reinforced anti-corrosion composite bar and a preparation method thereof.
Background
Fiber reinforced composites (FRPs) are high performance materials formed by mixing fiber materials and matrix materials in a certain ratio and compounding by a certain process. The material has many excellent characteristics of light weight, high strength, corrosion resistance, easy cutting and the like, and has been widely applied to the fields of reinforcement and reconstruction of civil engineering structures and performance enhancement through years of development. The composite bar is a common fiber reinforced composite material, which is a high-performance composite building material product formed by taking high-performance fibers as a reinforcing material and resin as a matrix material through a stretch winding process, and the market demand and the performance requirements of people are higher and higher.
The existing reinforcing material for the composite bar is mainly carbon fiber and glass fiber, and the carbon fiber has the best performance but higher cost; the glass fiber has poor wear resistance and high energy consumption in the production process, and is unfavorable for energy conservation and environmental protection. It is under this circumstance that basalt fiber reinforced composite tendons have been developed. The basalt fiber is a novel inorganic environment-friendly green high-performance fiber material, has wide sources, low price and balanced performance, is well combined with a common resin system, and the composite bar produced by using the basalt fiber has high strength and high cost performance; however, the basalt fiber reinforced composite bar in the market has the technical defects of insufficient ageing resistance, strong brittleness, high price, further improvement of corrosion resistance, insufficient performance stability caused by the compatibility problem between the fiber material and the matrix material, and the like.
In order to solve the problems, china patent No. 201410290224.0 discloses a basalt fiber composite rib and a preparation method thereof, wherein the basalt fiber composite rib is a fiber rib material formed by processing basalt fibers by a surface treatment agent, then impregnating and solidifying by matrix resin, the basalt fibers are made of roving or composite twisted roving for textile processing, the diameter of the basalt fibers is 7-13 mu m, and the preparation method comprises three steps of fiber surface treatment, matrix resin impregnation and solidification molding. The invention overcomes a plurality of defects existing in the existing glass fiber manufacturing process, adopts the operation steps of brushing, dipping, vacuum pressurizing, drying and the like, has simple and quick manufacturing steps, can realize industrialized mass production, and has low manufacturing cost. However, the composite bar still has the technical problems that the ageing resistance and the corrosion resistance are required to be further improved.
Therefore, a more effective method is sought, the basalt fiber reinforced composite bar with good corrosion resistance, good mechanical property, excellent aging resistance and long service life is prepared, meets the market demand, has wide market value and application prospect, and has very important significance for promoting the development of the basalt fiber reinforced composite bar field.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the basalt fiber reinforced corrosion-resistant composite bar with good corrosion resistance, good mechanical property, excellent ageing resistance and long service life and the preparation method thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme: the basalt fiber reinforced corrosion-resistant composite bar comprises the following raw materials in parts by weight: 15-25 parts of resin matrix, 75-85 parts of basalt fiber, 4-8 parts of curing agent, 3-5 parts of coupling agent and 4-6 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1 (1-3): 0.8-1.2): 0.4.
Preferably, the resin matrix is a mixture formed by mixing Atla c epoxy bisphenol A vinyl resin and hyperbranched perfluoropolyether polyurethane acrylic acid oligomer according to the mass ratio of (3-5): 1.
Preferably, the source of the hyperbranched perfluoropolyether urethane acrylic oligomer is not particularly required, and in one embodiment of the present invention, the hyperbranched perfluoropolyether urethane acrylic oligomer is prepared according to the method of example 1 of the chinese patent application publication No. CN 105482680B.
Preferably, the basalt fiber is made of roving or composite twisted roving for textile processing, and the average diameter of the basalt fiber is 5-15 mu m.
Preferably, the curing agent is a mixture formed by mixing Butanox LPT and Accelerator NL-51P according to the mass ratio of (2-4): 1.
Preferably, the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH 570.
The invention further aims at providing a preparation method of the basalt fiber reinforced corrosion-resistant composite bar, which comprises the following steps:
step S1, uniformly mixing the raw materials in parts by weight to obtain a glue solution, and dipping the basalt fiber subjected to yarn pulling in the glue solution to obtain a basalt fiber containing glue;
Step S2, after the basalt fiber containing the glue, which is manufactured in the step S1, is intertwined, sand blasting is carried out by quartz sand;
And S3, after solidification and shaping, cutting to obtain the basalt fiber reinforced corrosion-resistant composite bar.
Preferably, in the step S2, the mass ratio of the basalt fiber containing the glue to the quartz sand is (150-160): 3-6.
Preferably, the particle size of the quartz sand in the step S2 is 30-60 meshes.
Preferably, the solidification and shaping in the step S3 is performed by heating and solidifying through a pultrusion die, wherein the pultrusion speed is 590-630 mm/min, the traction force is 0.45-0.65 t, the pressure is 0.7-1.1 Mpa, and the temperature is 100-112 ℃.
Due to the application of the technical scheme, the invention has the following beneficial effects:
(1) The preparation method of the basalt fiber reinforced corrosion-resistant composite bar disclosed by the invention has the advantages of simple process, convenient operation control, high preparation efficiency and finished product qualification rate, small dependence on equipment, suitability for continuous large-scale production and higher popularization and application values.
(2) The invention discloses a basalt fiber reinforced corrosion-resistant composite bar which is prepared from the following raw materials in parts by weight: 15-25 parts of resin matrix, 75-85 parts of basalt fiber, 4-8 parts of curing agent, 3-5 parts of coupling agent and 4-6 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1 (1-3): 0.8-1.2): 0.4. Through reasonable selection of the resin matrix composition, the compatibility of the resin matrix composition and basalt fibers can be improved, the compatibility can be further improved through the addition of a coupling agent, the compactness of the internal structure of the material is further improved, and the technical defects that the product performance stability is insufficient and the service life is influenced due to phase separation caused by the compatibility problem between inorganic and organic raw materials are avoided. The resin matrix is a mixture formed by mixing Atlac 430 epoxy bisphenol A vinyl resin and hyperbranched perfluoropolyether polyurethane acrylic acid oligomer according to the mass ratio of (3-5) to 1, the matrix materials containing unsaturated olefinic bonds can be subjected to curing reaction with components containing unsaturated olefinic bonds in other components under the action of a curing agent to form an interpenetrating network structure, and meanwhile, epoxy groups on 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione can also be subjected to epoxy ring-opening reaction with amino groups on 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone in other components; the introduced bisphenol A, hyperbranched perfluoropolyether polyurethane, tetraoxaspiro [5.5] undecane, triazinetrione, borazine and fluorine-containing diphenyl sulfone structure have the advantages of good corrosion resistance, good mechanical properties, excellent aging resistance and long service life under the multiple actions of electronic effect, steric effect and conjugation effect.
(3) The basalt fiber reinforced corrosion resistant composite bar disclosed by the invention is added with other components, and the other components are defined as a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluorodiphenyl sulfone according to the mass ratio of 1 (1-3): (0.8-1.2): 0.4. Through reasonable selection of the components and the dosage, a matrix with a specific structure and an interpenetrating network structure can be formed, and further the advantages of good corrosion resistance, good mechanical properties, excellent ageing resistance and long service life of the composite reinforcement product are endowed. Through reasonable selection of technological parameters in the preparation process, the energy consumption can be effectively reduced, and the performance of the product can be further improved.
Detailed Description
The following description is presented to enable one of ordinary skill in the art to make and use the invention. The preferred embodiments in the following description are by way of example only and other obvious variations will occur to those skilled in the art.
Example 1
The basalt fiber reinforced corrosion-resistant composite bar comprises the following raw materials in parts by weight: 15 parts of resin matrix, 75 parts of basalt fiber, 4 parts of curing agent, 3 parts of coupling agent and 4 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1:1:0.8:0.4.
The resin matrix is a mixture formed by mixing Atla c epoxy bisphenol A vinyl resin and hyperbranched perfluoropolyether polyurethane acrylic acid oligomer according to the mass ratio of 3:1; the hyperbranched perfluoropolyether polyurethane acrylic acid oligomer is prepared according to the method of the Chinese invention patent example 1 with the authorized bulletin number of CN 105482680B; the basalt fiber is made of roving, and the average diameter of the basalt fiber is 5 mu m; the curing agent is a mixture formed by mixing Butanox LPT and Accelerator NL-51P according to a mass ratio of 2:1; the coupling agent is a silane coupling agent KH550.
The preparation method of the basalt fiber reinforced corrosion-resistant composite bar comprises the following steps:
step S1, uniformly mixing the raw materials in parts by weight to obtain a glue solution, and dipping the basalt fiber subjected to yarn pulling in the glue solution to obtain a basalt fiber containing glue;
Step S2, after the basalt fiber containing the glue, which is manufactured in the step S1, is intertwined, sand blasting is carried out by quartz sand;
And S3, after solidification and shaping, cutting to obtain the basalt fiber reinforced corrosion-resistant composite bar.
In the step S2, the mass ratio of the basalt fiber containing the glue to the quartz sand is 150:3; the particle size of the quartz sand in the step S2 is 30 meshes; the solidification shaping in the step S3 is formed by heating and solidifying a pultrusion mould, wherein the pultrusion speed is 590mm/min, the traction force is 0.45t, the pressure is 0.7Mpa, and the temperature is 100 ℃.
Example 2
The basalt fiber reinforced corrosion-resistant composite bar comprises the following raw materials in parts by weight: 17 parts of resin matrix, 77 parts of basalt fiber, 5 parts of curing agent, 3.5 parts of coupling agent and 4.5 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1:1.5:0.9:0.4.
The resin matrix is a mixture formed by mixing Atla c epoxy bisphenol A vinyl resin and hyperbranched perfluoropolyether polyurethane acrylic acid oligomer according to the mass ratio of 3.5:1; the hyperbranched perfluoropolyether polyurethane acrylic acid oligomer is prepared according to the method of the Chinese invention patent example 1 with the authorized bulletin number of CN 105482680B; the basalt fiber is made of composite twisted roving for textile processing, and the average diameter of the basalt fiber is 8 mu m; the curing agent is a mixture formed by mixing Butanox LPT and Accelerator NL-51P according to a mass ratio of 2.5:1; the coupling agent is silane coupling agent KH560.
The preparation method of the basalt fiber reinforced corrosion-resistant composite bar comprises the following steps:
step S1, uniformly mixing the raw materials in parts by weight to obtain a glue solution, and dipping the basalt fiber subjected to yarn pulling in the glue solution to obtain a basalt fiber containing glue;
Step S2, after the basalt fiber containing the glue, which is manufactured in the step S1, is intertwined, sand blasting is carried out by quartz sand;
And S3, after solidification and shaping, cutting to obtain the basalt fiber reinforced corrosion-resistant composite bar.
In the step S2, the mass ratio of the basalt fiber containing the glue to the quartz sand is 153:4; the particle size of the quartz sand in the step S2 is 40 meshes; the solidification shaping in the step S3 is formed by heating and solidifying a pultrusion mould, wherein the pultrusion speed is 600mm/min, the traction force is 0.5t, the pressure is 0.8Mpa, and the temperature is 104 ℃.
Example 3
The basalt fiber reinforced corrosion-resistant composite bar comprises the following raw materials in parts by weight: 20 parts of resin matrix, 80 parts of basalt fiber, 6 parts of curing agent, 4 parts of coupling agent and 5 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1:2:1:0.4.
The resin matrix is a mixture formed by mixing Atla c epoxy bisphenol A vinyl resin and hyperbranched perfluoropolyether polyurethane acrylic acid oligomer according to a mass ratio of 4:1; the hyperbranched perfluoropolyether polyurethane acrylic acid oligomer is prepared according to the method of the Chinese invention patent example 1 with the authorized bulletin number of CN 105482680B; the basalt fiber is made of roving, and the average diameter of the basalt fiber is 10 mu m; the curing agent is a mixture formed by mixing Butanox LPT and Accelerator NL-51P according to a mass ratio of 3:1; the coupling agent is a silane coupling agent KH570.
The preparation method of the basalt fiber reinforced corrosion-resistant composite bar comprises the following steps:
step S1, uniformly mixing the raw materials in parts by weight to obtain a glue solution, and dipping the basalt fiber subjected to yarn pulling in the glue solution to obtain a basalt fiber containing glue;
Step S2, after the basalt fiber containing the glue, which is manufactured in the step S1, is intertwined, sand blasting is carried out by quartz sand;
And S3, after solidification and shaping, cutting to obtain the basalt fiber reinforced corrosion-resistant composite bar.
In the step S2, the mass ratio of the basalt fiber containing the glue to the quartz sand is 155:4.5; the particle size of the quartz sand in the step S2 is 45 meshes; the solidification shaping in the step S3 is formed by heating and solidifying a pultrusion mould, wherein the pultrusion speed is 610mm/min, the traction force is 0.55t, the pressure is 0.9Mpa, and the temperature is 108 ℃.
Example 4
The basalt fiber reinforced corrosion-resistant composite bar comprises the following raw materials in parts by weight: 23 parts of resin matrix, 83 parts of basalt fiber, 7 parts of curing agent, 4.5 parts of coupling agent and 5.5 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1:2.5:1.1:0.4.
The resin matrix is a mixture formed by mixing Atla c epoxy bisphenol A vinyl resin and hyperbranched perfluoropolyether polyurethane acrylic acid oligomer according to the mass ratio of 4.5:1; the hyperbranched perfluoropolyether polyurethane acrylic acid oligomer is prepared according to the method of the Chinese invention patent example 1 with the authorized bulletin number of CN 105482680B; the basalt fiber is made of composite twisted roving for textile processing, and the average diameter of the basalt fiber is 13 mu m; the curing agent is a mixture formed by mixing Butanox LPT and Accelerator NL-51P according to a mass ratio of 3.5:1; the coupling agent is a mixture formed by mixing a silane coupling agent KH550, a silane coupling agent KH560 and a silane coupling agent KH570 according to a mass ratio of 1:2:3.
The preparation method of the basalt fiber reinforced corrosion-resistant composite bar comprises the following steps:
step S1, uniformly mixing the raw materials in parts by weight to obtain a glue solution, and dipping the basalt fiber subjected to yarn pulling in the glue solution to obtain a basalt fiber containing glue;
Step S2, after the basalt fiber containing the glue, which is manufactured in the step S1, is intertwined, sand blasting is carried out by quartz sand;
And S3, after solidification and shaping, cutting to obtain the basalt fiber reinforced corrosion-resistant composite bar.
In the step S2, the mass ratio of the basalt fiber containing the glue to the quartz sand is 158:5; the particle size of the quartz sand in the step S2 is 50 meshes; the solidification shaping in the step S3 is formed by heating and solidifying a pultrusion mould, wherein the pultrusion speed is 620mm/min, the traction force is 0.6t, the pressure is 1Mpa, and the temperature is 110 ℃.
Example 5
The basalt fiber reinforced corrosion-resistant composite bar comprises the following raw materials in parts by weight: 25 parts of resin matrix, 85 parts of basalt fiber, 8 parts of curing agent, 5 parts of coupling agent and 6 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1:3:1.2:0.4.
The resin matrix is a mixture formed by mixing 3835:1 of Atla c epoxy bisphenol A vinyl resin and hyperbranched perfluoropolyether polyurethane acrylic acid oligomer according to the mass ratio; the hyperbranched perfluoropolyether polyurethane acrylic acid oligomer is prepared according to the method of the Chinese invention patent example 1 with the authorized bulletin number of CN 105482680B; the basalt fiber is made of roving, and the average diameter of the basalt fiber is 15 mu m; the curing agent is a mixture formed by mixing Butanox LPT and Accelerator NL-51P according to a mass ratio of 4:1; the coupling agent is a silane coupling agent KH550.
The preparation method of the basalt fiber reinforced corrosion-resistant composite bar comprises the following steps:
step S1, uniformly mixing the raw materials in parts by weight to obtain a glue solution, and dipping the basalt fiber subjected to yarn pulling in the glue solution to obtain a basalt fiber containing glue;
Step S2, after the basalt fiber containing the glue, which is manufactured in the step S1, is intertwined, sand blasting is carried out by quartz sand;
And S3, after solidification and shaping, cutting to obtain the basalt fiber reinforced corrosion-resistant composite bar.
In the step S2, the mass ratio of the basalt fiber containing the glue to the quartz sand is 160:6; the particle size of the quartz sand in the step S2 is 60 meshes; the solidification shaping in the step S3 is formed by heating and solidifying a pultrusion mould, wherein the pultrusion speed is 630mm/min, the traction force is 0.65t, the pressure is 1.1Mpa, and the temperature is 112 ℃.
Comparative example 1
This example provides a basalt fiber reinforced corrosion resistant composite bar substantially the same as example 1 except that 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluorodiphenyl sulfone were not added.
Comparative example 2
This example provides a basalt fiber-reinforced corrosion-resistant composite bar, which is substantially the same as example 1, except that 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane and 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1 h,3h,5 h) -trione are not added.
In order to further illustrate the beneficial technical effects of the basalt fiber reinforced corrosion resistant composite bars according to the embodiments of the present invention, the basalt fiber reinforced corrosion resistant composite bars according to embodiments 1 to 5 and comparative examples 1 to 2 were subjected to a related performance test; the test method is as follows: tensile properties and alkali resistance (strength retention) were tested based on JT/T776.4-2010; the aging resistance test is to put each basalt fiber reinforced anti-corrosion composite bar in hot air at 85 ℃ for manual accelerated aging for 100 hours, cool the bar to room temperature, test the tensile strength according to JT/T776.4-2010 again, and measure the aging resistance according to the retention rate of the tensile strength, wherein the larger the value is, the better the aging resistance is.
As can be seen from Table 1, the basalt fiber reinforced corrosion resistant composite bars of the various embodiments of the present invention have higher mechanical properties, aging resistance and corrosion resistance, and the addition of 2,4, 6-trivinyl boroxine, 3 '-diamino-4, 4' -difluorodiphenyl sulfone, 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane and 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione is beneficial for improving the above properties.
The above embodiments are provided for illustrating the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the present invention and to implement the same, and are not intended to limit the scope of the present invention, but any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (4)

1. The basalt fiber reinforced corrosion-resistant composite bar is characterized by comprising the following raw materials in parts by weight: 15-25 parts of resin matrix, 75-85 parts of basalt fiber, 4-8 parts of curing agent, 3-5 parts of coupling agent and 4-6 parts of other components; the other components are a mixture formed by mixing 3, 9-divinyl-2, 4,8, 10-tetraoxaspiro [5.5] undecane, 1, 3-bis (oxiranylmethyl) -5- (2-propenyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, 2,4, 6-trivinyl boroxine and 3,3 '-diamino-4, 4' -difluoro diphenyl sulfone according to the mass ratio of 1 (1-3): 0.8-1.2): 0.4; the resin matrix is a mixture formed by mixing Atlac 430 epoxy bisphenol A vinyl resin and hyperbranched perfluoropolyether polyurethane acrylic acid oligomer according to the mass ratio of (3-5): 1.
2. The basalt fiber reinforced corrosion resistant composite bar according to claim 1, wherein the basalt fiber is made of roving or composite twisted roving for textile processing, and has an average diameter of 5 to 15 μm.
3. The basalt fiber reinforced corrosion resistant composite bar according to claim 1, wherein the curing agent is a mixture formed by mixing Butanox LPT and Accelerator NL-51P according to a mass ratio of (2-4): 1.
4. The basalt fiber reinforced corrosion resistant composite bar of claim 1, wherein the coupling agent is at least one of a silane coupling agent KH550, a silane coupling agent KH560, and a silane coupling agent KH 570.
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