CN115160729A - Corrosion-resistant flame-retardant thermosetting composite material - Google Patents
Corrosion-resistant flame-retardant thermosetting composite material Download PDFInfo
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 230000007797 corrosion Effects 0.000 title claims abstract description 30
- 238000005260 corrosion Methods 0.000 title claims abstract description 30
- 239000003063 flame retardant Substances 0.000 title claims abstract description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 52
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000000835 fiber Substances 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 24
- 239000003822 epoxy resin Substances 0.000 claims abstract description 23
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 239000005011 phenolic resin Substances 0.000 claims abstract description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 13
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 12
- 239000010445 mica Substances 0.000 claims abstract description 12
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 3
- 241000196324 Embryophyta Species 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 15
- 240000008564 Boehmeria nivea Species 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229920002748 Basalt fiber Polymers 0.000 claims description 8
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical group CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 8
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 8
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 7
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- -1 polydimethylsiloxane Polymers 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000012783 reinforcing fiber Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 244000198134 Agave sisalana Species 0.000 claims description 2
- 240000006240 Linum usitatissimum Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000945 filler Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920001342 Bakelite® Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000027734 detection of oxygen Effects 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a corrosion-resistant flame-retardant thermosetting composite material, and relates to the technical field of thermosetting material processing. The thermosetting composite material is mainly prepared by compounding and mixing raw materials such as thermosetting phenolic resin, modified epoxy resin, modified plant fiber, reinforced fiber, a carbon nanotube, a curing agent, multi-stage particle size silica powder, mica powder, nano aluminum hydroxide powder, toner, an antioxidant and the like. The invention overcomes the defects of the prior art, effectively ensures the excellent mechanical property of the material, improves the corrosion resistance and the flame retardance of the material, has simple processing and low cost, and comprehensively improves the application range and the market value of the material.
Description
Technical Field
The invention relates to the technical field of thermosetting material processing, in particular to a corrosion-resistant flame-retardant thermosetting composite material.
Background
The thermosetting composite material is prepared by using a thermosetting polymer as a matrix resin and appropriately adding a filler, such as glass fiber reinforced plastic, bakelite and the like. The filler used for preparing the thermosetting composite material at present usually comprises calcium carbonate, alumina, talcum powder, bentonite, mica, graphite, glass flakes and the like, and is mainly used for improving the mechanical property and the strength of the material.
Because thermosetting composite material range of application is extensive, also increasingly high to its performance requirement, when guaranteeing the mechanical properties of material basis, promote the corrosion-resistant of material, flame retardant effect is also extremely important, most direct addition has corrosion-resistant or fire retardant ability among thermosetting resin among the prior art, because there is the difference in the combination dispersion effect between different auxiliary materials and resin, finally lead to the performance of material unbalanced easily, simultaneously because the addition of auxiliary material can cause the change of composite material mechanical properties, make the comprehensive properties of material reduce to some extent, cause the range of application of material to reduce, can reduce the life and the security of material simultaneously, bring certain puzzlement for practical application.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the corrosion-resistant flame-retardant thermosetting composite material, which effectively ensures the excellent mechanical property of the material, improves the corrosion resistance and the flame retardance of the material, is simple to process and low in cost, and comprehensively improves the application range and the market value of the material.
In order to realize the purpose, the invention is realized by the following technical scheme:
the corrosion-resistant flame-retardant thermosetting composite material is prepared from the following raw materials in parts by weight: 20-30 parts of thermosetting phenolic resin, 20-30 parts of modified epoxy resin, 4-6 parts of modified plant fiber, 3-6 parts of reinforcing fiber, 3-6 parts of carbon nano-tube, 2-4 parts of curing agent, 10-15 parts of multi-stage particle size silicon dioxide powder, 20-30 parts of mica powder, 20-50 parts of nano aluminum hydroxide powder, 1-2 parts of toner and 1-3 parts of antioxidant.
Preferably, the modified epoxy resin is obtained by mixing bisphenol A epoxy resin with tetrabutyl titanate for reaction, and then adding hydroxyl-terminated polydimethylsiloxane and tetraethoxysilane for modification treatment.
Preferably, the mass ratio of the bisphenol A epoxy resin, the butyl titanate, the hydroxyl-terminated polydimethylsiloxane and the tetraethoxysilane in the modified epoxy resin is 16: 2: 1: 0.7.
Preferably, in the multistage-particle-size silicon dioxide powder, silicon dioxide with the particle size of 1-100nm accounts for 20% of the total amount, silicon dioxide with the particle size of 1-30 μm accounts for 40% of the total amount, and silicon dioxide with the particle size of 31-120 μm accounts for 40% of the total amount.
Preferably, the modified plant fiber is obtained by alternately soaking the plant fiber in acid solution with the pH of 6-6.5 and alkali solution with the pH of 8-8.5.
Preferably, the plant fiber is any one of ramie fiber, sisal fiber and flax fiber.
Preferably, the reinforcing fibers are mixed fibers of basalt fibers and glass fibers in a mass ratio of 1: 2.
Preferably, the curing agent is a mixture of p-methanesulfonic acid and tert-butyl perbenzoate in a mass ratio of 2: 1.
Preferably, the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the toner is titanium dioxide.
Preferably, the preparation method of the thermosetting composite material comprises the following steps:
(1) Compounding auxiliary materials: dispersing carbon nanotubes, multi-stage particle size silica powder, mica powder and nano aluminum hydroxide powder in ethanol solution, mixing with modified plant fiber, stirring, and centrifugally drying to obtain auxiliary materials for later use;
(2) Mixing raw materials: and fully mixing the thermosetting phenolic resin, the modified epoxy resin, the reinforcing fiber, the auxiliary materials, the toner, the antioxidant and the curing agent in a mixing roll to obtain the thermosetting composite material.
The invention provides a corrosion-resistant flame-retardant thermosetting composite material, which has the following advantages compared with the prior art:
(1) The thermosetting phenolic resin and the modified epoxy resin are adopted as base materials, wherein the thermosetting phenolic resin has excellent flame retardance, insulation and acid and alkali resistance, the epoxy resin also has a certain acid and alkali resistance effect, and meanwhile, auxiliary materials can be compounded through various polar groups and active epoxy groups contained in the thermosetting phenolic resin, but the raw materials have certain brittleness after being cured, meanwhile, the epoxy resin is relatively inflammable one of the thermosetting phenolic resin, and the epoxy resin is modified through n-butyl titanate, hydroxyl-terminated polydimethylsiloxane and tetraethoxysilane, so that the flame retardance and toughness of the material are comprehensively improved, and the basic mechanical property of the material is improved.
(2) According to the invention, through the addition of components such as multi-stage particle size silicon dioxide powder, modified plant fiber, carbon nano-tube and aluminum hydroxide nano-powder, the thermosetting phenolic resin and the modified epoxy resin are compounded, so that the flame retardant and corrosion resistant effects of the final thermosetting composite material can be effectively ensured, wherein the plant fiber is subjected to acid-base treatment, so that compact pores are formed on the surface of the plant fiber, and the silicon dioxide with different particle sizes and fillers of various powders are matched, so that the thermosetting phenolic resin and the modified epoxy resin can be fully dispersed, the fillers are prevented from agglomerating, the uniform flame retardant and corrosion resistant properties of the material are ensured, meanwhile, the stability of a fiber framework is improved through the combination of the fillers and fiber components, and the mechanical properties of the subsequent material are further improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described below clearly and completely in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
1. preparation of modified epoxy resin:
according to the mass ratio of 16: 2: 1: 0.7, preparing bisphenol A epoxy resin, butyl orthotitanate, hydroxyl-terminated polydimethylsiloxane and tetraethoxysilane, mixing the bisphenol A epoxy resin with the butyl orthotitanate, stirring uniformly at a high speed, adding the hydroxyl-terminated polydimethylsiloxane and tetraethoxysilane, boosting the pressure to 8MPa, adjusting the rotation speed to 1200r/min, and continuously stirring and modifying for 2 hours to obtain the modified epoxy resin.
2. Preparing modified plant fibers:
stirring and soaking ramie fibers in acid liquor with the pH value of 6-6.5 for 20min, taking out the ramie fibers, washing the ramie fibers with ethanol, drying the ramie fibers, adding alkali liquor with the pH value of 8-8.5, continuing to soak the ramie fibers for 20min, taking out the ramie fibers, washing the ramie fibers with ethanol, and drying the ramie fibers to obtain the modified plant fibers.
3. Preparing the silicon dioxide powder with the multilevel particle size:
mixing the silicon dioxide particles with the particle sizes of 1-100nm, 1-30 mu m and 31-120 mu m according to the mass ratio of 1: 2 to obtain the multi-level particle size silicon dioxide powder.
Example 2:
preparing the corrosion-resistant flame-retardant thermosetting composite material:
(1) Preparing auxiliary materials: ultrasonic dispersing 30g of carbon nanotubes, 100g of the multi-stage particle size silica powder prepared in the example 1, 200g of mica powder and 200g of nano aluminum hydroxide powder in an ethanol solution for 5min, mixing 40g of the modified plant fibers prepared in the example 1, uniformly stirring, centrifuging, and drying at 80-100 ℃ to constant weight to obtain auxiliary materials for later use;
(2) Mixing raw materials: 200g of a thermosetting phenol resin, 200g of the modified epoxy resin prepared in example 1, 10g of basalt fiber, 20g of glass fiber, 10g of titanium dioxide, 10g of 2, 6-di-tert-butyl-4-methylphenol, 7g of methanesulfonic acid, 14g of tert-butyl perbenzoate, and the above auxiliary materials were mixed in a kneader and sufficiently kneaded for 4 hours, thereby obtaining a thermosetting composite material.
Example 3:
preparing the corrosion-resistant flame-retardant thermosetting composite material:
(1) Preparing auxiliary materials: carrying out ultrasonic dispersion on 60g of carbon nanotubes, 150g of the multi-stage particle size silica powder prepared in the example 1, 300g of mica powder and 500g of nano aluminum hydroxide powder in an ethanol solution for 5min, then mixing 60g of the modified plant fibers prepared in the example 1, uniformly stirring, centrifuging, and drying at 100 ℃ to constant weight to obtain auxiliary materials for later use;
(2) Mixing raw materials: a thermosetting phenol resin (300 g), a modified epoxy resin (300 g) prepared in example 1, basalt fiber (20 g), glass fiber (40 g), titanium dioxide (20 g), 2, 6-di-tert-butyl-4-methylphenol (30 g), methanesulfonic acid (13 g), tert-butyl perbenzoate (26 g) and the above-mentioned auxiliary materials were mixed in a kneader and sufficiently kneaded for 4 hours to obtain a thermosetting composite material.
Example 4:
preparing the corrosion-resistant flame-retardant thermosetting composite material:
(1) Preparing auxiliary materials: carrying out ultrasonic dispersion on 45g of carbon nanotubes, 120g of the multi-stage particle size silica powder prepared in the example 1, 250g of mica powder and 350g of nano aluminum hydroxide powder in an ethanol solution for 5min, then mixing 50g of the modified plant fibers prepared in the example 1, uniformly stirring, centrifuging, and drying at the temperature of 80-100 ℃ to constant weight to obtain auxiliary materials for later use;
(2) Mixing raw materials: 250g of a thermosetting phenol resin, 250g of the modified epoxy resin prepared in example 1, 15g of basalt fiber, 30g of glass fiber, 15g of titanium dioxide, 20g of 2, 6-di-tert-butyl-4-methylphenol, 10g of methanesulfonic acid, 20g of tert-butyl perbenzoate and the above-mentioned auxiliary materials were mixed in a mixer and sufficiently kneaded for 4 hours to obtain a thermosetting composite material.
Comparative example 1:
preparation of the thermosetting composite material:
(1) Preparing auxiliary materials: ultrasonically dispersing 45g of carbon nanotubes, 120g of silica powder with the particle size of 31-120 mu m, 250g of mica powder and 350g of nano aluminum hydroxide powder in an ethanol solution for 5min, mixing 50g of ramie fibers, uniformly stirring, centrifuging, and drying at 80-100 ℃ to constant weight to obtain auxiliary materials for later use;
(2) Mixing raw materials: 250g of a thermosetting phenol resin, 250g of the modified epoxy resin prepared in example 1, 15g of basalt fiber, 30g of glass fiber, 15g of titanium dioxide, 20g of 2, 6-di-tert-butyl-4-methylphenol, 10g of methanesulfonic acid, 20g of tert-butyl perbenzoate and the above-mentioned auxiliary materials were mixed in a mixer and sufficiently kneaded for 4 hours to obtain a thermosetting composite material.
Comparative example 2:
preparation of the thermosetting composite material:
(1) Preparing auxiliary materials: ultrasonically dispersing 45g of carbon nanotubes, 120g of the multi-stage particle size silica powder prepared in the embodiment 1, 250g of mica powder and 350g of nano aluminum hydroxide powder in an ethanol solution for 5min, then mixing 50g of ramie fibers, uniformly stirring, centrifuging, and drying at the temperature of 80-100 ℃ to constant weight to obtain auxiliary materials for later use;
(2) Mixing raw materials: 250g of thermosetting phenolic resin, 250g of bisphenol A epoxy resin, 15g of basalt fiber, 30g of glass fiber, 15g of titanium dioxide, 20g of 2, 6-di-tert-butyl-4-methylphenol, 10g of methanesulfonic acid, 20g of tert-butyl perbenzoate and the auxiliary materials are mixed in a mixing roll and fully mixed for 4 hours to obtain the thermosetting composite material.
Comparative example 3:
preparation of the thermosetting composite material:
(1) Preparing auxiliary materials: ultrasonically dispersing 45g of carbon nanotubes, 120g of silica powder with the particle size of 31-120 mu m, 250g of mica powder and 350g of nano aluminum hydroxide powder in an ethanol solution for 5min, mixing 50g of ramie fibers, uniformly stirring, centrifuging, and drying at 80-100 ℃ to constant weight to obtain auxiliary materials for later use;
(2) Mixing raw materials: 250g of thermosetting phenolic resin, 250g of bisphenol A epoxy resin, 15g of basalt fiber, 30g of glass fiber, 15g of titanium dioxide, 20g of 2, 6-di-tert-butyl-4-methylphenol, 10g of methanesulfonic acid, 20g of tert-butyl perbenzoate and the auxiliary materials are mixed in a mixing roll and fully mixed for 4 hours to obtain the thermosetting composite material.
And (3) detection:
1. the mechanical properties of the thermosetting composite materials prepared in the above examples 2 to 4 and comparative examples 1 to 3 were measured, and the specific results are shown in the following table 1:
TABLE 1
As can be seen from the above table, in the embodiments 2 to 4 of the present invention, the mechanical properties of the material can be effectively improved by adding the multi-stage particle size silica powder, the modified plant fiber, and the modified epoxy resin.
2. The thermosetting composite materials prepared in the above examples 2-4 and comparative examples 1-3 were subjected to flame retardancy (detection of oxygen index of each group of materials) and corrosion resistance (detection of corrosion rate of each group of materials after being soaked in 10% hydrochloric acid, 20% acetic acid and 30% sulfuric acid solution for 4 hours, wherein the corrosion rate = (mass before soaking-mass after soaking)/mass before soaking), and the specific results are shown in the following table 2:
TABLE 2
As can be seen from the above table, the flame retardant effect of the material can be effectively ensured and the corrosion resistance of the material can be improved by adding the multi-stage particle size silica powder, the modified plant fiber and the modified epoxy resin in embodiments 2 to 4 of the present invention.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrases "comprising a," "8230," "8230," or "comprising" does not exclude the presence of additional like elements in a process, method, article, or apparatus that comprises the element.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The corrosion-resistant flame-retardant thermosetting composite material is characterized by being prepared from the following raw materials in parts by weight: 20-30 parts of thermosetting phenolic resin, 20-30 parts of modified epoxy resin, 4-6 parts of modified plant fiber, 3-6 parts of reinforcing fiber, 3-6 parts of carbon nano-tube, 2-4 parts of curing agent, 10-15 parts of multi-stage particle size silica powder, 20-30 parts of mica powder, 20-50 parts of nano aluminum hydroxide powder, 1-2 parts of toner and 1-3 parts of antioxidant.
2. The corrosion-resistant flame-retardant thermoset composite material according to claim 1, wherein: the modified epoxy resin is obtained by mixing bisphenol A epoxy resin with tetrabutyl titanate for reaction, and then adding hydroxyl-terminated polydimethylsiloxane and tetraethoxysilane for modification treatment.
3. A corrosion resistant flame retardant thermoset composite material in accordance with claim 2, wherein: the mass ratio of bisphenol A epoxy resin, tetrabutyl titanate, hydroxyl-terminated polydimethylsiloxane and tetraethoxysilane in the modified epoxy resin is 16: 2: 1: 0.7.
4. The corrosion-resistant flame-retardant thermoset composite material according to claim 1, wherein: in the multistage-particle-size silicon dioxide powder, silicon dioxide with the particle size of 1-100nm accounts for 20% of the total amount, silicon dioxide with the particle size of 1-30 mu m accounts for 40% of the total amount, and silicon dioxide with the particle size of 31-120 mu m accounts for 40% of the total amount.
5. The corrosion-resistant flame-retardant thermoset composite material according to claim 1, wherein: the modified plant fiber is obtained by alternately soaking plant fiber in acid solution with pH of 6-6.5 and alkali solution with pH of 8-8.5.
6. The corrosion-resistant flame-retardant thermosetting composite material according to claim 5, wherein: the plant fiber is any one of ramie fiber, sisal fiber and flax fiber.
7. A corrosion resistant flame retardant thermoset composite material in accordance with claim 1, wherein: the reinforced fiber is a mixed fiber of basalt fiber and glass fiber in a mass ratio of 1: 2.
8. A corrosion resistant flame retardant thermoset composite material in accordance with claim 1, wherein: the curing agent is a mixture of the methanesulfonic acid and the perbenzoic acid tert-butyl ester in a mass ratio of 2: 1.
9. A corrosion resistant flame retardant thermoset composite material in accordance with claim 1, wherein: the antioxidant is 2, 6-di-tert-butyl-4-methylphenol, and the toner is titanium dioxide.
10. The corrosion-resistant flame-retardant thermosetting composite material according to claim 1, wherein the preparation method of the thermosetting composite material comprises the following steps:
(1) Compounding auxiliary materials: dispersing carbon nanotubes, multi-stage particle size silica powder, mica powder and nano aluminum hydroxide powder in ethanol solution, mixing with modified plant fiber, stirring, and centrifugally drying to obtain auxiliary materials for later use;
(2) Mixing raw materials: and fully mixing the thermosetting phenolic resin, the modified epoxy resin, the reinforcing fiber, the auxiliary materials, the toner, the antioxidant and the curing agent in a mixing roll to obtain the thermosetting composite material.
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