CN113292819B - Epoxy resin composition capable of being quickly cured at medium and low temperature, epoxy resin matrix composite material and preparation method thereof - Google Patents
Epoxy resin composition capable of being quickly cured at medium and low temperature, epoxy resin matrix composite material and preparation method thereof Download PDFInfo
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- CN113292819B CN113292819B CN202110234566.0A CN202110234566A CN113292819B CN 113292819 B CN113292819 B CN 113292819B CN 202110234566 A CN202110234566 A CN 202110234566A CN 113292819 B CN113292819 B CN 113292819B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 141
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 141
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 239000011159 matrix material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000000945 filler Substances 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 51
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 27
- 239000012745 toughening agent Substances 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims description 31
- 239000003365 glass fiber Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 25
- 238000007598 dipping method Methods 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 239000005995 Aluminium silicate Substances 0.000 claims description 16
- 235000012211 aluminium silicate Nutrition 0.000 claims description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 16
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC(C)C)OC1=CC=CC=C1 RYUJRXVZSJCHDZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 11
- 239000010425 asbestos Substances 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 10
- 230000000149 penetrating effect Effects 0.000 claims description 10
- 229910052895 riebeckite Inorganic materials 0.000 claims description 10
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 5
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 4
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 113
- 238000000034 method Methods 0.000 abstract description 13
- 230000009477 glass transition Effects 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 6
- 238000013035 low temperature curing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 description 32
- 239000011347 resin Substances 0.000 description 32
- 238000005470 impregnation Methods 0.000 description 9
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 239000010453 quartz Substances 0.000 description 6
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- 235000019359 magnesium stearate Nutrition 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- 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 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4223—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aromatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
-
- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
- C08K7/12—Asbestos
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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)
- Dispersion Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a medium-low temperature fast-curing epoxy resin composition, an epoxy resin matrix composite material and a preparation method thereof, wherein the medium-low temperature fast-curing epoxy resin composition comprises the following components in parts by mass: 100 parts of epoxy resin, 0.1-5 parts of imidazole accelerator, 2-40 parts of filler, 30-200 parts of anhydride curing agent, 1-40 parts of toughening agent and 0.5-10 parts of release agent. According to the epoxy resin composition and the epoxy resin matrix composite material capable of being rapidly cured at medium and low temperatures and the preparation method thereof, through the cooperation of the raw materials such as the anhydride curing agent and the imidazole accelerator in the epoxy resin composition, the medium and low temperature curing time of the epoxy resin matrix composite material can be obviously shortened, the pultrusion speed of the composite material in a pultrusion process is obviously improved, and the composite material is excellent in mechanical property and high in glass transition temperature.
Description
Technical Field
The invention belongs to the technical field of epoxy resin-based composite materials, and particularly relates to an epoxy resin composition capable of being quickly cured at medium and low temperatures, an epoxy resin-based composite material and a preparation method thereof.
Background
Epoxy resin is an advanced composite resin matrix, and has excellent properties, particularly in terms of wear resistance, mechanical properties, adhesion, chemical stability, electrical insulation, adhesion to a substrate, and the like, so that the epoxy resin can be seen in the fields of machinery, chemical industry, construction, railway transportation, aerospace, and the like. The epoxy resin-based fiber reinforced composite material has excellent performance, light weight and high strength, and is suitable for various molding and processing technologies. The pultrusion process is to continuously produce glass fiber reinforced plastic profiles with unlimited length by molding and solidifying continuous fiber bundles, belts or cloths impregnated with resin glue solution through an extrusion die under the action of traction force. The epoxy resin-based continuous fiber pultrusion technology has the advantages of easy industrial continuous production, high production efficiency, multiple modes and pieces, full play of the mechanical properties of continuous fibers, stable product properties and the like, and is rapidly developed in recent years. Along with the development of the composite material pultrusion industry market, the internal competition of the industry is more and more vigorous, and under the situation, the speed and the cost are accelerated and reduced to become the first choice of various composite material manufacturers.
In the prior art, the epoxy resin matrix material has high general viscosity, when thick-wall products are produced, the conventional method is adopted to increase the pultrusion speed, so that poor impregnation of fibers in the products is easily caused, the mechanical properties of the products are reduced, even the rejection rate is increased, and unnecessary waste is generated; and the glass transition temperature of the epoxy resin matrix material is low, the curing temperature is higher, and the curing speed is low at medium and low temperatures, so that the production efficiency of the epoxy resin composite material is lower.
Disclosure of Invention
The invention solves the technical problems of providing an epoxy resin composition capable of being quickly cured at medium and low temperature, an epoxy resin-based composite material and a preparation method thereof, and the epoxy resin composition has the advantages that the medium and low temperature curing time of the epoxy resin-based composite material can be obviously shortened by matching raw materials such as an anhydride curing agent, an imidazole accelerator and the like in the epoxy resin composition, the pultrusion speed of the composite material in a pultrusion process is obviously improved, the mechanical property of the composite material is excellent, and the glass transition temperature is high.
In order to solve the above problems, an aspect of the present invention provides a medium-low temperature fast-curing epoxy resin composition comprising, in parts by mass:
100 parts of epoxy resin, 0.1-5 parts of imidazole accelerator, 2-40 parts of filler, 30-200 parts of anhydride curing agent, 1-40 parts of toughening agent and 0.5-10 parts of release agent.
The epoxy resin composition for medium and low temperature rapid curing adopts the imidazole accelerator and the anhydride curing agent to compound, the curing behavior of the epoxy resin composition belongs to anionic catalytic polymerization, and chain transfer does not exist at high temperature, so that the medium and low temperature curing speed of the epoxy resin composition is higher, and the vitrification temperature is higher.
Preferably, the medium-low temperature fast-curing epoxy resin composition comprises the following components in parts by weight:
100 parts of epoxy resin, 0.2-2 parts of imidazole accelerator, 5-20 parts of filler, 80-100 parts of anhydride curing agent, 2-20 parts of toughening agent and 1-5 parts of release agent.
When the formula range of the mass parts is adopted, the pultrusion speed of the obtained epoxy resin composition in the pultrusion production process can be obviously improved, and the internal fiber of the product is immersed in the glue solution at a high speed, with good immersing effect, optimal mechanical property and high glass transition temperature. In the preferred formula range, the pultrusion speed of the epoxy resin composite material thick-wall product can be increased to 0.3m/min, the mechanical property of the product is stable, and no dry yarn exists in the product; in addition, the glass transition temperature of the product can reach 130 ℃.
Preferably, the anhydride-based curing agent is a low viscosity anhydride-based curing agent having a viscosity of 100-300mpa.s at 25 ℃. The invention adopts the low-viscosity acid anhydride curing agent, and can play a role of a diluent for the epoxy resin composition, obviously reduce the viscosity of the resin glue solution, and improve the fiber impregnation speed in the production process, thereby improving the pultrusion speed of the composite material in the pultrusion process and improving the impregnation effect.
Preferably, the low-viscosity anhydride curing agent is one or a mixture of more of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride.
Preferably, the filler comprises a first filler, a second filler, a third filler, and a fourth filler;
the first filler is one or a mixture of two of kaolin and calcined kaolin;
the second filler is one or a mixture of more of asbestos powder and quartz powder;
the third filler is silica gel powder;
the fourth filler is diphenyl isodecyl phosphate.
In the epoxy resin composition for medium-low temperature rapid curing, the interaction of various fillers in the filler and the resin matrix is mainly realized through physical adsorption, namely electrostatic force. In the filler, the kaolin and the calcined kaolin can improve the resin content of the product, reduce the production cost and have little influence on the viscosity of the epoxy resin glue solution; asbestos powder, quartz powder and stone powder in the filler can reduce the shrinkage rate of the product during molding and ensure the stability of the interface size of the product; the silica gel powder in the filler can better improve the heat resistance of the epoxy resin composite material and has positive contribution to the glass transition temperature. The diphenyl isodecyl phosphate in the filler can further improve the flame retardant and toughening effects of the epoxy resin composition.
Preferably, in the filler, the mass ratio of the first filler, the second filler, the third filler and the fourth filler is 1: (4-5): (3-4): (5-7).
A large number of experimental attempts show that when the above proportion of four fillers is selected, the obtained epoxy resin composition has the advantages of optimal mechanical property, highest impregnation speed, best impregnation effect, greatly improved pultrusion speed, higher curing speed at medium and low temperature and highest glass transition temperature.
Preferably, the imidazole accelerator is one or a mixture of more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole and 2, 4-dimethylimidazole.
Preferably, the toughening agent is one or a mixture of a plurality of dioctyl phthalate, dibutyl phthalate, triphenyl phosphate and tricresyl phosphate.
Preferably, the release agent is one or a mixture of more of barium stearate, calcium stearate, magnesium stearate and zinc stearate.
Another aspect of the present invention provides a method for preparing the above-described medium-low temperature fast-curing epoxy resin composition, comprising the steps of:
mixing and stirring the epoxy resin, the imidazole accelerator, the filler, the anhydride curing agent, the toughening agent and the release agent to obtain the intermediate-low temperature fast-curing epoxy resin composition.
Preferably, the method for preparing the medium-low temperature fast-curing epoxy resin composition comprises the following steps:
s1, adding the filler, the toughening agent and the release agent into the epoxy resin according to the selected mass portion, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20min;
s2, adding the imidazole accelerator and the anhydride curing agent into the product obtained in the step S1, and stirring for 10-20min at the rotating speed of 1000-1500r/min to obtain the epoxy resin composition which is rapidly cured at medium and low temperature.
In yet another aspect, the present invention provides an epoxy resin-based composite material comprising:
the resin matrix is the epoxy resin composition which is quickly cured at medium and low temperature.
Preferably, the reinforcing material is glass fiber or carbon fiber.
In still another aspect, the present invention provides a method for preparing the epoxy resin-based composite material described above, comprising the steps of:
and impregnating the reinforcing material into the resin matrix, and then adopting a pultrusion process to mold and cure to obtain the epoxy resin matrix composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the epoxy resin composition for medium-low temperature rapid curing, the imidazole accelerator and the anhydride curing agent are compounded, the curing behavior of the epoxy resin composition belongs to anionic catalytic polymerization, and chain transfer does not exist at high temperature, so that the medium-low temperature curing speed of the epoxy resin composition is higher, and the vitrification temperature is higher; the low-viscosity acid anhydride curing agent is adopted, so that the low-viscosity acid anhydride curing agent can play a role of a diluent for the epoxy resin composition, and obviously reduce the viscosity of the resin glue solution, so that the fiber impregnation speed in the production process can be increased, the pultrusion speed of the composite material in the pultrusion process is increased, and the impregnation effect of the composite material is also improved;
2. the formula of the epoxy resin composition which is quickly cured at medium and low temperature is further optimized, so that the pultrusion speed of the obtained epoxy resin composition in the pultrusion production process is obviously improved, and the product has the advantages of high impregnation speed of internal fibers in glue solution, good impregnation effect, optimal mechanical property of the product and high glass transition temperature. In the preferable formula range, the pultrusion speed of the epoxy resin composite material thick-wall product can be increased to 0.3m/min, the mechanical property of the product is stable, and no dry yarn exists in the product; in addition, the glass transition temperature of the product can reach 130 ℃.
3. The intermediate-low temperature fast-curing epoxy resin composition mainly interacts with various fillers in the filler and the resin matrix through physical adsorption, namely electrostatic force. In the filler, the kaolin and the calcined kaolin can improve the resin content of the product, reduce the production cost and have little influence on the viscosity of the epoxy resin glue solution; asbestos powder, quartz powder and stone powder in the filler can reduce the shrinkage rate of the product during molding and ensure the stability of the interface size of the product; the silica gel powder in the filler can better improve the heat resistance of the epoxy resin composite material and has positive contribution to the glass transition temperature. The diphenyl isodecyl phosphate in the filler can further improve the flame retardant and toughening effects of the epoxy resin composition.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The epoxy resin composition for medium and low temperature rapid curing according to the embodiment comprises the following components:
100 parts of epoxy resin, 1 part of imidazole accelerator 2-ethyl-4-methylimidazole, 10 parts of filler, 90 parts of anhydride curing agent methyl hexahydrophthalic anhydride, 10 parts of toughening agent dioctyl phthalate and 2 parts of release agent calcium stearate. Wherein the filler comprises kaolin, asbestos powder, silica gel powder and diphenyl isodecyl phosphate in a mass ratio of 1:4:3:5.5.
The preparation method of the epoxy resin composition capable of being rapidly cured at medium and low temperature in the embodiment specifically comprises the following steps:
s1, adding the filler, the toughening agent and the release agent into the epoxy resin according to the selected mass portion, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20min;
s2, adding an imidazole accelerator and an anhydride curing agent into the product obtained in the step S1, and stirring for 10-20min at the rotating speed of 1000-1500r/min to obtain the epoxy resin composition which is rapidly cured at medium and low temperature.
The epoxy resin-based composite material of the present embodiment includes: the obtained medium-low temperature fast-curing epoxy resin composition resin matrix and glass fiber reinforced material are glass fiber pultrusion yarns with the product model of EDR960-T911, which are purchased from Taishan glass fiber company; the product has linear density of 2400+ -120 tex, water content less than or equal to 0.10%, and combustible content of 0.40-0.70%.
The preparation method comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating chart, then dipping the glass fiber reinforced materials in the obtained intermediate-low temperature fast-curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front zone curing temperature is 110-120 ℃, and the rear zone curing temperature is 130-140 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.25m/min, and obtaining the epoxy resin matrix composite material.
Example 2
The epoxy resin composition for medium and low temperature rapid curing according to the embodiment comprises the following components:
100 parts of epoxy resin, 1.5 parts of imidazole accelerator 2, 4-dimethyl imidazole, 10 parts of filler, 90 parts of anhydride curing agent methyltetrahydrophthalic anhydride, 10 parts of toughening agent methyltetrahydrophthalic anhydride and 2 parts of release agent magnesium stearate. Wherein the filler comprises kaolin, asbestos powder, silica gel powder and diphenyl isodecyl phosphate with the mass ratio of 1:4.5:3.5:6.5.
The preparation method of the epoxy resin composition capable of being rapidly cured at medium and low temperature in the embodiment specifically comprises the following steps:
s1, adding the filler, the toughening agent and the release agent into the epoxy resin according to the selected mass portion, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20min;
s2, adding an imidazole accelerator and an anhydride curing agent into the product obtained in the step S1, and stirring for 10-20min at the rotating speed of 1000-1500r/min to obtain the epoxy resin composition which is rapidly cured at medium and low temperature.
The epoxy resin-based composite material of the present embodiment includes: the obtained medium-low temperature fast-curing epoxy resin composition resin matrix and glass fiber reinforced material.
The preparation method comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating chart, then dipping the glass fiber reinforced materials in the obtained intermediate-low temperature fast-curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 67%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front zone curing temperature is 105-115 ℃, and the rear zone curing temperature is 135-145 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.27m/min, and obtaining the epoxy resin matrix composite material.
Example 3
The epoxy resin composition for medium and low temperature rapid curing according to the embodiment comprises the following components:
100 parts of epoxy resin, 2 parts of imidazole accelerator 2-methylimidazole, 10 parts of filler, 90 parts of anhydride curing agent 2-methylimidazole, 10 parts of toughening agent triphenyl phosphate and 2 parts of release agent zinc stearate. Wherein the filler comprises calcined kaolin, asbestos powder, silica gel powder and diphenyl isodecyl phosphate with the mass ratio of 1:5:3.5:6.
The preparation method of the epoxy resin composition capable of being rapidly cured at medium and low temperature in the embodiment specifically comprises the following steps:
s1, adding the filler, the toughening agent and the release agent into the epoxy resin according to the selected mass portion, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20min;
s2, adding an imidazole accelerator and an anhydride curing agent into the product obtained in the step S1, and stirring for 10-20min at the rotating speed of 1000-1500r/min to obtain the epoxy resin composition which is rapidly cured at medium and low temperature.
The epoxy resin-based composite material of the present embodiment includes: the obtained medium-low temperature fast-curing epoxy resin composition resin matrix and glass fiber reinforced material.
The preparation method comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating chart, then dipping the glass fiber reinforced materials in the obtained intermediate-low temperature fast-curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front zone curing temperature is 110-120 ℃, and the rear zone curing temperature is 130-140 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.3m/min, and obtaining the epoxy resin matrix composite material.
Example 4
The epoxy resin composition for medium and low temperature rapid curing according to the embodiment comprises the following components:
100 parts of epoxy resin, 0.5 part of imidazole accelerator 2-ethylimidazole, 10 parts of filler, 90 parts of anhydride curing agent tetrahydrophthalic anhydride, 10 parts of toughening agent tricresyl phosphate and 2 parts of release agent barium stearate. Wherein the filler comprises calcined kaolin, asbestos powder, silica gel powder and diphenyl isodecyl phosphate with the mass ratio of 1:4.5:4:5.5.
The preparation method of the epoxy resin composition capable of being rapidly cured at medium and low temperature in the embodiment specifically comprises the following steps:
s1, adding the filler, the toughening agent and the release agent into the epoxy resin according to the selected mass portion, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20min;
s2, adding an imidazole accelerator and an anhydride curing agent into the product obtained in the step S1, and stirring for 10-20min at the rotating speed of 1000-1500r/min to obtain the epoxy resin composition which is rapidly cured at medium and low temperature.
The epoxy resin-based composite material of the present embodiment includes: the obtained medium-low temperature fast-curing epoxy resin composition resin matrix and glass fiber reinforced material.
The preparation method comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating chart, then dipping the glass fiber reinforced materials in the obtained intermediate-low temperature fast-curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front zone curing temperature is 105-115 ℃, and the rear zone curing temperature is 130-140 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.3m/min, and obtaining the epoxy resin matrix composite material.
Example 5
The epoxy resin composition for medium and low temperature rapid curing according to the embodiment comprises the following components:
100 parts of epoxy resin, 0.2 part of imidazole accelerator 2-methylimidazole, 5 parts of filler, 100 parts of anhydride curing agent methyl hexahydrophthalic anhydride, 20 parts of toughening agent dibutyl phthalate and 1 part of release agent magnesium stearate. Wherein the filler comprises calcined kaolin, quartz powder, silica gel powder and diphenyl isodecyl phosphate with the mass ratio of 1:4.5:3:6.
The method for preparing the intermediate-low temperature rapid-curing epoxy resin composition of this example was the same as in example 1.
The preparation method of the epoxy resin-based composite material comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating chart, then dipping the glass fiber reinforced materials in the obtained intermediate-low temperature fast-curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 67%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front zone curing temperature is 100-110 ℃, and the rear zone curing temperature is 140-150 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.2m/min, and obtaining the epoxy resin matrix composite material.
Example 6
The epoxy resin composition for medium and low temperature rapid curing according to the embodiment comprises the following components:
100 parts of epoxy resin, 2 parts of imidazole accelerator 2-ethylimidazole, 20 parts of filler, 80 parts of anhydride curing agent methyl hexahydrophthalic anhydride, 2 parts of toughening agent dibutyl phthalate and 5 parts of release agent barium stearate. Wherein the filler comprises calcined kaolin, quartz powder, silica gel powder and diphenyl isodecyl phosphate with the mass ratio of 1:4.5:3.5:6.5.
The method for preparing the intermediate-low temperature rapid-curing epoxy resin composition of this example was the same as in example 1.
The preparation method of the epoxy resin-based composite material comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating chart, then dipping the glass fiber reinforced materials in the obtained intermediate-low temperature fast-curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front zone curing temperature is 110-120 ℃, and the rear zone curing temperature is 140-150 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.27m/min, and obtaining the epoxy resin matrix composite material.
Example 7
The epoxy resin composition for medium and low temperature rapid curing according to the embodiment comprises the following components:
100 parts of epoxy resin, 0.1 part of imidazole accelerator 2, 4-dimethyl imidazole, 40 parts of filler, 200 parts of anhydride curing agent methyltetrahydrophthalic anhydride, 1 part of toughening agent tricresyl phosphate and 0.5 part of release agent zinc stearate. Wherein the filler comprises kaolin, quartz powder, silica gel powder and diphenyl isodecyl phosphate in a mass ratio of 1:4:3:5.
The method for preparing the intermediate-low temperature rapid-curing epoxy resin composition of this example was the same as in example 1.
The preparation method of the epoxy resin-based composite material comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating chart, then dipping the glass fiber reinforced materials in the obtained intermediate-low temperature fast-curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front zone curing temperature is 130-140 ℃, and the rear zone curing temperature is 150-160 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.15m/min, and obtaining the epoxy resin matrix composite material.
Example 8
The epoxy resin composition for medium and low temperature rapid curing according to the embodiment comprises the following components:
100 parts of epoxy resin, 5 parts of imidazole accelerator 2, 4-dimethyl imidazole, 2 parts of filler, 30 parts of anhydride curing agent methyltetrahydrophthalic anhydride, 40 parts of toughening agent dioctyl phthalate and 10 parts of release agent barium stearate. Wherein the filler comprises calcined kaolin, asbestos powder, silica gel powder and diphenyl isodecyl phosphate with the mass ratio of 1:4.5:3:5.5.
The method for preparing the intermediate-low temperature rapid-curing epoxy resin composition of this example was the same as in example 1.
The preparation method of the epoxy resin-based composite material comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating chart, then dipping the glass fiber reinforced materials in the obtained intermediate-low temperature fast-curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 67%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front zone curing temperature is 130-140 ℃, and the rear zone curing temperature is 160-170 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.12m/min, so as to obtain the epoxy resin-based composite material.
Comparative example
The epoxy resin composition of this comparative example comprises the following components:
100 parts of epoxy resin, 10 parts of filler, 90 parts of anhydride curing agent methyl hexahydrophthalic anhydride, 10 parts of toughening agent dibutyl phthalate and 2 parts of release agent magnesium stearate. Wherein the filler comprises kaolin, asbestos powder, silica gel powder and diphenyl isodecyl phosphate in a mass ratio of 1:4:3:5.
The preparation method of the epoxy resin composition of this comparative example is the same as that of example 1.
The preparation method of the epoxy resin-based composite material of the comparative example comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a yarn penetrating diagram, then dipping the glass fiber reinforced materials in the obtained epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 70%, then preforming, and carrying out extrusion molding and curing, traction, cutting and product preparation, wherein the curing stage adopts zonal curing, the front curing temperature is 140-150 ℃, and the rear curing temperature is 170-180 ℃; and drawing by adopting a reciprocating type drawing extruder, wherein the drawing speed is 0.08m/min, and obtaining the epoxy resin matrix composite material.
Epoxy resin based composite material performance test
The mechanical properties and glass transition temperatures of the epoxy resin-based composite materials obtained in the examples and comparative examples were measured, and the measurement results are shown in table 1 below.
TABLE 1
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (1)
1. An epoxy-based composite material, comprising:
an epoxy resin composition and a glass fiber reinforced material which are rapidly cured at medium and low temperatures;
the epoxy resin composition capable of being rapidly cured at medium and low temperature comprises the following components: 100 parts of epoxy resin, 0.5 part of imidazole accelerator 2-ethylimidazole, 10 parts of filler, 90 parts of anhydride curing agent tetrahydrophthalic anhydride, 10 parts of toughening agent tricresyl phosphate and 2 parts of release agent barium stearate; wherein the filler comprises calcined kaolin, asbestos powder, silica gel powder and diphenyl isodecyl phosphate with the mass ratio of 1:4.5:4:5.5;
the preparation method of the epoxy resin composition capable of being rapidly cured at medium and low temperature comprises the following steps:
s1, adding the filler, the toughening agent and the release agent into the epoxy resin according to the selected mass portion, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20min;
s2, adding an imidazole accelerator and an anhydride curing agent into the product obtained in the step S1, and stirring for 10-20min at the rotating speed of 1000-1500r/min to obtain the epoxy resin composition which is rapidly cured at medium and low temperature;
the preparation method of the epoxy resin-based composite material comprises the following steps: arranging a glass fiber reinforced material according to a yarn penetrating chart, then dipping in the epoxy resin composition which is rapidly cured at a medium and low temperature, wherein the volume fraction of the epoxy resin composition after dipping is 65%, then preforming, and obtaining an epoxy resin matrix composite material through extrusion molding, curing, traction, cutting and product; wherein, the curing stage adopts zonal curing, the curing temperature of the front zone is 105-115 ℃ and the curing temperature of the rear zone is 130-140 ℃; pulling by a reciprocating type pultrusion machine, wherein the pultrusion speed is 0.3m/min.
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