CN106398119B - A kind of fibre-reinforced bio-resin glue composite material and preparation method - Google Patents

A kind of fibre-reinforced bio-resin glue composite material and preparation method Download PDF

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CN106398119B
CN106398119B CN201610791868.7A CN201610791868A CN106398119B CN 106398119 B CN106398119 B CN 106398119B CN 201610791868 A CN201610791868 A CN 201610791868A CN 106398119 B CN106398119 B CN 106398119B
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parts
bio
resin glue
fibre
composite
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CN106398119A (en
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曹海波
王兴财
王维平
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Sichuan Jingwen Material Technology Co., Ltd
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Sichuan Gaoneng Hi-Tech Biological Resin Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/04Ingredients characterised by their shape and organic or inorganic ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/10Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised against heat, light or radiation or oxydation

Abstract

The present invention discloses a kind of fibre-reinforced bio-resin glue composite material and preparation method, and the composite material is made of the raw material including following parts by weight:10-50 parts of bio-resin glue, 50-100 parts of fiber, the bio-resin glue are made of the raw material including following parts by weight:20-100 parts of bio-oil modified epoxy, 2-20 parts of diluent, 1-4 parts of emulsifier, 1-3 parts of coupling agent, 1-5 parts of releasing agent, 5-20 parts of filler, 1-4 parts of pigment, 10-20 parts of curing accelerator.After the fibre-reinforced bio-resin glue composite material prepares bio-resin glue using bio-oil modified epoxy as raw material, then wetting fibre is cured, obtain that toughness is more preferable, and weather resistance is more preferable, the composite material of every excellent in mechanical performance.Composite material is prepared using this method, raw material is cheap and easy to get, simple production process and it is ripe, and reduce the cost of composite material.

Description

A kind of fibre-reinforced bio-resin glue composite material and preparation method
Technical field
The present invention relates to composite material and its production technical fields, and in particular to a kind of fibre-reinforced bio-resin glue is multiple Condensation material and preparation method thereof.
Background technology
Fibre reinforced composites are by reinforcing fiber materials and basis material through receiving and distributing paste, winding, molding or pultrusion etc. Moulding process and the composite material formed.According to the difference of reinforcing material, common fibre reinforced composites are divided into glass fibers Dimension enhancing composite material, basalt fibre reinforcing composite material, carbon fibre reinforced composite and aramid fiber enhancing are compound Material.Fibre reinforced composites have following features:(1) specific strength is high, and specific modulus is big;(2) material property has and can design Property;(3) corrosion resistance and endurance quality are good;(4) coefficient of thermal expansion and concrete is close.These features so that fiber reinforcement is multiple Condensation material can meet modern structure to greatly across, towering, heavily loaded, high-strength light and needs of job development under severe conditions, The requirement of modern architecture construction industriesization development can also be met simultaneously, therefore be applied to various civilian build more and more widely Build, bridge, highway, ocean, hydro-structure, underground structure, in the fields such as rail traffic and aerospace.
By basis material difference, fibre reinforced composites can be divided into resin base, Metal Substrate and ceramic matric composite.Tree Resin-based composite mainly has thermosetting resin based composites and thermoplastic resin based composite material two major classes, wherein thermosetting property Polymer matrix composites refer to that for example unsaturated polyester resin, epoxy resin, phenolic resin is matrixes using thermosetting resin, with glass Fiber, carbon fiber, aramid fiber etc. are composite material made of reinforcing material, and the composite material corresponding to them is referred to as not Saturated polyester composite material, epoxy resin composite material and phenolic resin.Due to unsaturated polyester (UP), epoxy resin and phenolic resin Excellent chemical stability, electrical insulating property, corrosion resistance, good adhesive property and higher mechanical strength are all had, extensively Applied to every field such as chemical industry, light industry, machinery, electronics, water conservancy, traffic, automobile, household electrical appliances and aerospace.Epoxy resin has excellent Adhesive property and its use of good physical mechanical and electrical insulation capability, corrosion resistance, chemical stability and a variety of materials The features such as flexibility of technique, is widely used in and prepares composite material, but epoxy resin brittleness is big, poor impact resistance, is easy Cracking, not ageing-resistant etc., these defects greatly limit them in those ageing-resistant and high impact-resistants of needs and resist Application under fracture property occasion.
Invention content
In view of this, the application provides a kind of fibre-reinforced bio-resin glue composite material and preparation method, it is described Fibre-reinforced bio-resin glue composite material prepares bio-resin glue using bio-oil modified epoxy as raw material, then After wetting fibre is cured, obtain that toughness is more preferable, and weather resistance is more preferable, the composite material of every excellent in mechanical performance.Using This method prepares composite material, and raw material is cheap and easy to get, simple production process and it is ripe, and reduce the cost of composite material.
In order to solve the above technical problems, technical solution provided by the invention is that a kind of fibre-reinforced bio-resin glue is compound Material, the composite material are made of the raw material including following parts by weight:10-50 parts of bio-resin glue, fiber 50-100 Part, the bio-resin glue is made of the raw material including following parts by weight:20-100 parts of bio-oil modified epoxy, 2-20 parts of diluent, 1-4 parts of emulsifier, 1-3 parts of coupling agent, 1-5 parts of releasing agent, 5-20 parts of filler, 1-4 parts of pigment, 10-20 parts of curing accelerator.
Preferably, the composite material is made of the raw material including following parts by weight:20-40 parts of biomass resin glue, 60-80 parts of fiber, the bio-resin glue are made of the raw material including following parts by weight:Bio-oil modified epoxy 50-100 parts, 3-6 parts of diluent, 2-3 parts of emulsifier, 1.5-2.5 parts of coupling agent, 2-4 parts of releasing agent, 6-8 parts of filler, 2-3 parts of pigment, 12-16 parts of curing accelerator.
Preferably, the biology that the bio-oil modified epoxy is lignin, cellulose, hemicellulose crack Matter oil is modified epoxy resin by the method for chemistry.The cost of epoxy resin can be reduced, asphalt mixtures modified by epoxy resin is improved Toughness, shock resistance anti-cracking performance and the weather resistance of fat.
More preferably, the diluent is at least one selected from ethyl alcohol, n-butanol, butyl acetate, ethyl acetate, tetrahydrochysene Furans, ethylene glycol, glycerine;The emulsifier is at least one selected from sorbitan trioleate, sorbitol polyoxyethylene Six stearate of ether, glycol fatty acid ester, methyl glycol fatty acid ester, glycerin monostearate, anhydrous sorbitol monostearate Ester, diethylene glycol aliphatic ester, polyoxyethylene oxypropylene oleate.
More preferably, the coupling agent is at least one selected from silane coupling agent, zirconium class coupling agent, titanate esters coupling Agent.
More preferably, the releasing agent is at least one selected from zinc stearate, calcium stearate, dimethicone, methyl Phenyl silicone oil, silicone emulsion.
More preferably, the curing accelerator be it is at least one selected from 2- dimethylaminomethylphenols, dimethylaniline, Triethylenediamine, pyridine, triethanolamine, N- 2-glycidyl aniline.
More preferably, the pigment is that any one is selected from titanium dioxide, iron oxide red, iron oxide yellow, carbon black, chrome green; Filler is at least one selected from calcined kaolin, bentonite, titanium dioxide, calcium carbonate, aluminium hydroxide, magnesium hydroxide, barium sulfate, illiteracy De- stone.
Preferably, the fiber is that any one is selected from glass fibre, basalt fibre, carbon fiber, aramid fiber.
A kind of preparation method of above-mentioned fibre-reinforced bio-resin glue composite material of the technical scheme offer, The preparation method comprises the following steps:
(1) bio-oil modified epoxy, diluent, emulsifier, coupling agent, releasing agent, filler, pigment, solidification are taken Accelerating agent sequentially adds stirred tank, stirs 10-20min, stirs evenly, obtain bio-resin glue;
(2) fiber for accounting for total fiber mass 33.3-100% is taken, the bio-resin glue is added and is infiltrated, forms leaching Moisten fiber;
(3) wetting fibre for obtaining step (2) is blended with residual fiber, and is evenly distributed;
(4) wetting fibre and residual fiber step (3) being evenly distributed are together by die material, by being centainly molded The fibre-reinforced bio-resin glue composite material is made in technique.
Preferably, the wetting fibre and the mixing proportion of the residual fiber are not less than 1:2, the bio-resin glue The percentage that weight accounts for total fiber mass is no more than 40%.
Preferably, certain moulding process is that any one is selected from manual pasting forming process, pultrusion molding process, is wound in Type technique, die press technology for forming.
The feed diluent of composite material in technical scheme, releasing agent, emulsifier, coupling agent, filler, pigment, Curing accelerator and fiber derive from commercially available, and bio-oil modified epoxy is from commercially available.
A kind of preparation principle of fibre-reinforced bio-resin glue composite material described in technical scheme is:By two Kind or more material of different nature, make to occur physically or chemically to react between each component by the method for hot briquetting in mold, It makes up for each other's deficiencies and learn from each other in performance in macroscopic view or microcosmic upper material of the composition with new capability, a variety of materials, generates synergistic effect, The comprehensive performance of material is set to be better than former composition material and meet a variety of different requirements.
In technical scheme, the fibre-reinforced bio-resin glue composite material uses bio-oil modified epoxy Resin contains long alkyl chain as raw material, bio-oil, and the toughness after epoxy resin cure is made to increase, and solves conventional epoxy tree The big problem of brittleness after fat solidification, while the raising of resin toughness, further increase the adhesion to fiber to resin, make compound The mechanical strength of material shows more preferable;On the other hand, resin base material and compound can be improved in bio-oil modified epoxy The ageing-resistant performance of material.The preparation method is simple, therefore is more applicable for the production of composite material;Bio-oil modified epoxy tree For fat cost well below epoxy resin, its addition reduces composite material production costs.The fiber can be glass fibers Dimension, basalt fibre, carbon fiber or aramid fiber, their addition increase the intensity of composite material, improve composite material Corrosion resistance and fire-retardant, heat-insulated, insulation performance, while also reducing the cost of composite material.
Compared with prior art, the advantageous effect of technical scheme is:Fiber described in technical scheme increases Strong bio-resin glue composite material prepares bio-resin glue using bio-oil modified epoxy as raw material, then infiltrates fibre After dimension is cured, obtain that toughness is more preferable, and weather resistance is more preferable, the composite material of every excellent in mechanical performance.Using this method Prepare composite material, raw material is cheap and easy to get, simple production process and it is ripe, and reduce the cost of composite material.
Specific implementation mode
In order to make those skilled in the art more fully understand technical scheme of the present invention, with reference to specific embodiment pair The present invention is described in further detail.
Embodiment 1
A kind of fibre-reinforced bio-resin glue composite material described in the present embodiment, preparation method are:
(1) bio-resin glue is prepared:It counts in parts by weight, bio-oil is taken to be modified 100 parts of E44 epoxy resin, ethylene glycol 15 parts, 2 parts of polyoxyethylene oxypropylene oleate, 3 parts of calcium stearate, 1 part of Silane coupling agent KH550,10 parts of powdered whiting, 2 parts of iron oxide red, 15 parts of triethanolamine.Above-mentioned raw materials are added sequentially to stirred tank, wait stirring 10-20min uniform, are obtained biological Resin glue;
(2) 50 parts of glass fibre zero twisted yarns will be infiltrated in 30 parts of bio-resin glue injection size applicators, is formed Wetting fibre;
(3) wetting fibre is blended together with 20 parts of glass fibre zero twisted yarns again, and be evenly distributed;
(4) together by die material after being evenly distributed, by pultrusion molding process, being made has certain cross section shape A kind of fibre-reinforced bio-resin glue composite material of shape, dimensionally stable.
The Indexs measure result of above-mentioned fibre-reinforced bio-resin glue composite material is:Bending strength 726MPa, bending 5.22 × 104Mpa of modulus, impact flexibility 502KJ/m2, tensile strength 625MPa, 5.43 × 104Mpa of stretch modulus, fiber contains Amount 78.2%, density 1.982g/cm3, compressive strength 168MPa, bending strength retention 86.8% after ten period of humid heat treatment.
Reference examples 1 --- existing fibre-reinforced epoxide-resin glue composite material
Fibre-reinforced epoxide-resin glue composite material described in this reference examples, preparation method are:
(1) epoxide-resin glue is prepared:It counts in parts by weight, 100 parts of extracting epoxy resin E44,15 parts of ethylene glycol, polyoxy second 2 parts of alkene oxypropylene oleate, 3 parts of calcium stearate, 1 part of Silane coupling agent KH550,10 parts of powdered whiting, 2 parts of iron oxide red, 15 parts of triethanolamine.Above-mentioned raw materials are added sequentially to stirred tank, wait stirring 10-20min uniform, obtain epoxide-resin glue;
(2) 50 parts of glass fibre zero twisted yarns will be infiltrated in 30 parts of epoxide-resin glue injection size applicators, is formed Wetting fibre;
(3) wetting fibre is blended together with 20 parts of glass fibre zero twisted yarns again, and be evenly distributed;
(4) together by die material after being evenly distributed, by pultrusion molding process, being made has certain cross section shape A kind of fibre-reinforced epoxide-resin glue composite material of shape, dimensionally stable.
The Indexs measure result of above-mentioned fibre-reinforced epoxide-resin glue composite material is:Bending strength 563MPa, bending 3.95 × 104Mpa of modulus, impact flexibility 259KJ/m2, tensile strength 542MPa, 4.05 × 104Mpa of stretch modulus, fiber contains Amount 77.3%, density 1.971g/cm3, compressive strength 207MPa, bending strength retention 64.3% after ten period of humid heat treatment.
Embodiment 2
A kind of fibre-reinforced bio-resin glue composite material described in the present embodiment, preparation method are:
(1) bio-resin glue is prepared:It counts in parts by weight, bio-oil is taken to be modified 90 parts of F51 epoxy resin, ethyl alcohol 12 Part, 2.5 parts of diethylene glycol aliphatic ester, 2 parts of dimethicone, 1 part of silane coupling agent KH560,0 part of montmorillonite 2, carbon black 2 Part, 18 parts of pyridine.Above-mentioned raw materials are added sequentially to stirred tank, wait stirring 10-20min uniform, obtain bio-resin glue;
(2) 52 parts of glass fabrics will be infiltrated in 38 parts of bio-resin glue injection size applicators, forms infiltration Fiber;
(3) wetting fibre is mutually stacked together with 10 parts of basalt fiber cloths again, and be evenly distributed;
(4) together by die material after being evenly distributed, by die press technology for forming, being made has certain cross section shape A kind of fibre-reinforced bio-resin glue composite material of shape, dimensionally stable.
The Indexs measure result of above-mentioned fibre-reinforced bio-resin glue composite material is:Bending strength 378MPa, bending 2.17 × 104Mpa of modulus, impact flexibility 443KJ/m2, tensile strength 439MPa, 3.62 × 104Mpa of stretch modulus, fiber contains Amount 69.5%, density 1.785g/cm3, compressive strength 97MPa, bending strength retention 84.3% after ten period of humid heat treatment.
Reference examples 2 --- existing fibre-reinforced epoxide-resin glue composite material
Fibre-reinforced epoxide-resin glue composite material described in this reference examples, preparation method are:
(1) epoxide-resin glue is prepared:It counts in parts by weight, takes 90 parts of F51 epoxy resin, 12 parts of ethyl alcohol, diethylene glycol fat 2.5 parts of fat acid esters, 2 parts of dimethicone, 1 part of silane coupling agent KH560,0 part of montmorillonite 2,2 parts of carbon black, 18 parts of pyridine.It will Above-mentioned raw materials are added sequentially to stirred tank, wait stirring 10-20min uniform, obtain epoxide-resin glue;
(2) 52 parts of glass fabrics will be infiltrated in 38 parts of epoxide-resin glue injection size applicators, forms infiltration Fiber;
(3) wetting fibre is mutually stacked together with 10 parts of basalt fiber cloths again, and be evenly distributed;
(4) together by die material after being evenly distributed, by die press technology for forming, being made has certain cross section shape A kind of fibre-reinforced epoxide-resin glue composite material of shape, dimensionally stable.
The Indexs measure result of above-mentioned fibre-reinforced epoxide-resin glue composite material is:Bending strength 315MPa, bending 1.86 × 104Mpa of modulus, impact flexibility 328KJ/m2, tensile strength 363MPa, 2.12 × 104Mpa of stretch modulus, fiber contains Amount 68.9%, density 1.774g/cm3, compressive strength 124MPa, bending strength retention 62.7% after ten period of humid heat treatment.
Embodiment 3
A kind of fibre-reinforced bio-resin glue composite material described in the present embodiment, preparation method are:
(1) bio-resin glue is prepared:It counts in parts by weight, bio-oil is taken to be modified 85 parts of F44 epoxy resin, glycerine 17 Part, 1 part of sorbitan monostearate, 2 parts of polyoxyethylene oxypropylene oleate, 3 parts of zinc stearate, silane coupling agent 1.5 parts of KH550,10 parts of powdered whiting, 10 parts of montmorillonite, 2 parts of iron oxide red, 16 parts of N- 2-glycidyls aniline.It will be above-mentioned Raw material is added sequentially to stirred tank, waits stirring 10-20min uniform, obtains bio-resin glue;
(2) 40 parts of basalt fibre zero twisted yarns will be infiltrated in 25 parts of bio-resin glue injection size applicators, shape At wetting fibre;
(3) wetting fibre is mutually stacked together with 35 parts of basalt fibre zero twisted yarns again, and be evenly distributed;
(4) together by die material after being evenly distributed, by pultrusion molding process, being made has certain cross section shape A kind of fibre-reinforced bio-resin glue composite material of shape, dimensionally stable.
The Indexs measure result of above-mentioned fibre-reinforced bio-resin glue composite material is:Bending strength 868MPa, bending 6.91 × 104Mpa of modulus, impact flexibility 607KJ/m2, tensile strength 713MPa, 5.98 × 104Mpa of stretch modulus, fiber contains Amount 80.2%, density 2.27g/cm3, compressive strength 204MPa, bending strength retention 90.2% after ten period of humid heat treatment.
Reference examples 3 --- existing fibre-reinforced epoxide-resin glue composite material
Fibre-reinforced epoxide-resin glue composite material described in this reference examples, preparation method are:
(1) epoxide-resin glue is prepared:It counts in parts by weight, takes 85 parts of F44 epoxy resin, 17 parts of glycerine, Sorbitan 1 part of alcohol monostearate, 2 parts of polyoxyethylene oxypropylene oleate, 3 parts of zinc stearate, 1.5 parts of Silane coupling agent KH550, weight 10 parts of matter calcium carbonate, 10 parts of montmorillonite, 2 parts of iron oxide red, 16 parts of N- 2-glycidyls aniline.Above-mentioned raw materials are added sequentially to Stirred tank, waits stirring 10-20min uniform, obtains epoxide-resin glue;
(2) 40 parts of basalt fibre zero twisted yarns will be infiltrated in 25 parts of epoxide-resin glue injection size applicators, shape At wetting fibre;
(3) wetting fibre is mutually stacked together with 35 parts of basalt fibre zero twisted yarns again, and be evenly distributed;
(4) together by die material after being evenly distributed, by pultrusion molding process, being made has certain cross section shape A kind of fibre-reinforced epoxide-resin glue composite material of shape, dimensionally stable.
The Indexs measure result of above-mentioned fibre-reinforced epoxide-resin glue composite material is:Bending strength 664MPa, bending 5.35 × 104Mpa of modulus, impact flexibility 298KJ/m2, tensile strength 593MPa, 5.04 × 104Mpa of stretch modulus, fiber contains Amount 79.4%, density 2.21g/cm3, compressive strength 229MPa.Bending strength retention 65.9% after ten period of humid heat treatment.
Embodiment 4
A kind of fibre-reinforced bio-resin glue composite material described in the present embodiment, preparation method are:
(1) bio-resin glue is prepared:It counts in parts by weight, bio-oil is taken to be modified 80 parts of E51 epoxy resin, butanol 10 Part, 3 parts of methyl glycol fatty acid ester, 2 parts of zinc stearate, silane coupling agent, KH5601 parts of zirconium class coupling agent, aluminium hydroxide 10, hydrogen 5 parts of magnesia, 2 parts of iron oxide yellow, 13 parts of 2- dimethylaminomethylphenols.Above-mentioned raw materials are added sequentially to stirred tank, wait stirring 10-20min are uniform, obtain bio-resin glue;
(2) 45 parts of basalt fiber cloths will be infiltrated in 40 parts of bio-resin glue injection size applicators, forms leaching Moisten fiber;
(3) wetting fibre is mutually stacked together with 15 parts of basalt fiber cloths again, and be evenly distributed;
(4) together by die material after being evenly distributed, by die press technology for forming, being made has certain cross section shape A kind of fibre-reinforced bio-resin glue composite material of shape, dimensionally stable.
The Indexs measure result of above-mentioned fibre-reinforced bio-resin glue composite material is:Bending strength 469MPa, bending 3.78 × 104Mpa of modulus, impact flexibility 615KJ/m2, tensile strength 528MPa, 4.67 × 104Mpa of stretch modulus, fiber contains Amount 67.5%, density 1.938g/cm3, compressive strength 105MPa, bending strength retention 89.8% after ten period of humid heat treatment.
Reference examples 4 --- existing fibre-reinforced epoxide-resin glue composite material
Fibre-reinforced epoxide-resin glue composite material described in this reference examples, preparation method are:
(1) epoxide-resin glue is prepared:It counts in parts by weight, takes 80 parts of E51 epoxy resin, 10 parts of butanol, propylene glycol fatty 3 parts of acid esters, 2 parts of zinc stearate, silane coupling agent, 1 part of zirconium class coupling agent KH560, aluminium hydroxide 10,5 parts of magnesium hydroxide, oxygen Change 2 parts of iron oxide yellow, 13 parts of 2- dimethylaminomethylphenols.Above-mentioned raw materials are added sequentially to stirred tank, wait stirring 10-20min equal It is even, obtain epoxide-resin glue;
(2) 45 parts of basalt fiber cloths will be infiltrated in 40 parts of epoxide-resin glue injection size applicators, forms leaching Moisten fiber;
(3) wetting fibre is mutually stacked together with 15 parts of basalt fiber cloths again, and be evenly distributed;
(4) together by die material after being evenly distributed, by die press technology for forming, being made has certain cross section shape A kind of fibre-reinforced epoxide-resin glue composite material of shape, dimensionally stable.
The Indexs measure result of above-mentioned fibre-reinforced epoxide-resin glue composite material is:Bending strength 372MPa, bending 2.53 × 104Mpa of modulus, impact flexibility 404KJ/m2, tensile strength 401MPa, 3.52 × 104Mpa of stretch modulus, fiber contains Amount 67.8%, density 1.896g/cm3, compressive strength 136MPa.Bending strength retention 64.1% after ten period of humid heat treatment.
Preparation and experimental data from above example and reference examples can obtain, the fiber obtained by technical scheme The bio-resin glue composite material of enhancing, every Testing index is better than reference examples, and mechanical property is more excellent.
It the above is only the preferred embodiment of the present invention, it is noted that above-mentioned preferred embodiment is not construed as pair The limitation of the present invention, protection scope of the present invention should be subject to claim limited range.For the art For those of ordinary skill, without departing from the spirit and scope of the present invention, several improvements and modifications can also be made, these change Protection scope of the present invention is also should be regarded as into retouching.

Claims (9)

1. a kind of fibre-reinforced bio-resin glue composite material, it is characterised in that:The composite material is by including following weight The raw material of number is made:10-50 parts of bio-resin glue, 50-100 parts of fiber, the bio-resin glue is by including following weight The raw material of number is made:20-100 parts of bio-oil modified epoxy, 2-20 parts of diluent, 1-4 parts of emulsifier, coupling 1-3 parts of agent, 1-5 parts of releasing agent, 5-20 parts of filler, 1-4 parts of pigment, 10-20 parts of curing accelerator;
The fiber is that any one is selected from glass fibre, basalt fibre, carbon fiber, aramid fiber.
2. a kind of fibre-reinforced bio-resin glue composite material according to claim 1, it is characterised in that:It is described compound Material is made of the raw material including following parts by weight:20-40 parts of bio-resin glue, 60-80 parts of fiber, the bio-resin Glue is made of the raw material including following parts by weight:50-100 parts of bio-oil modified epoxy, 3-6 parts of diluent, breast 2-3 parts of agent, 1.5-2.5 parts of coupling agent, 2-4 parts of releasing agent, 6-8 parts of filler, 2-3 parts of pigment, curing accelerator 12- 16 parts.
3. a kind of fibre-reinforced bio-resin glue composite material according to claim 1 or 2, it is characterised in that:It is described Diluent is at least one selected from ethyl alcohol, n-butanol, butyl acetate, ethyl acetate, tetrahydrofuran, ethylene glycol, glycerine;It is described Emulsifier is at least one selected from sorbitan trioleate, six stearate of sorbitol polyoxyethylene ether, ethylene glycol fat Acid esters, methyl glycol fatty acid ester, glycerin monostearate, sorbitan monostearate, diethylene glycol aliphatic ester, polyoxy Ethylene oxypropylene oleate.
4. a kind of fibre-reinforced bio-resin glue composite material according to claim 1 or 2, it is characterised in that:It is described Coupling agent is at least one selected from silane coupling agent, zirconium class coupling agent, titanate coupling agent.
5. a kind of fibre-reinforced bio-resin glue composite material according to claim 1 or 2, it is characterised in that:It is described Releasing agent is at least one selected from zinc stearate, calcium stearate, dimethicone, methyl phenyl silicone oil, silicone emulsion.
6. a kind of fibre-reinforced bio-resin glue composite material according to claim 1 or 2, it is characterised in that:It is described Curing accelerator is at least one selected from 2- dimethylaminomethylphenols, dimethylaniline, triethylenediamine, pyridine, three second Hydramine, N- 2-glycidyl aniline.
7. a kind of fibre-reinforced bio-resin glue composite material according to claim 1 or 2, it is characterised in that:Filler It is de- selected from calcined kaolin, bentonite, titanium dioxide, calcium carbonate, aluminium hydroxide, magnesium hydroxide, barium sulfate, illiteracy at least one Stone;The pigment is that any one is selected from titanium dioxide, iron oxide red, iron oxide yellow, carbon black, chrome green.
8. a kind of preparation method of the fibre-reinforced bio-resin glue composite material of claim 1-7 any one of them, special Sign is:The preparation method comprises the following steps:
(1) bio-oil modified epoxy, diluent, emulsifier, coupling agent, releasing agent, filler, pigment, solidification is taken to promote Agent sequentially adds stirred tank, stirs 10-20min, stirs evenly, obtain bio-resin glue;
(2) fiber for accounting for total fiber mass 33.3-100% is taken, the bio-resin glue is added and is infiltrated, it is fine to form infiltration Dimension;
(3) wetting fibre for obtaining step (2) is blended with residual fiber, and is evenly distributed;
(4) wetting fibre and residual fiber step (3) being evenly distributed are together by die material, by being centainly molded work The fibre-reinforced bio-resin glue composite material is made in skill.
9. a kind of preparation method of fibre-reinforced bio-resin glue composite material according to claim 8, feature exist In:The wetting fibre and the mixing proportion of the residual fiber are not less than 1:2, it is total that the weight of the bio-resin glue accounts for fiber The percentage of quality is no more than 40%.
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