CN113292819A - Epoxy resin composition capable of being rapidly cured at medium and low temperature, epoxy resin-based composite material and preparation method thereof - Google Patents
Epoxy resin composition capable of being rapidly cured at medium and low temperature, epoxy resin-based composite material and preparation method thereof Download PDFInfo
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- CN113292819A CN113292819A CN202110234566.0A CN202110234566A CN113292819A CN 113292819 A CN113292819 A CN 113292819A CN 202110234566 A CN202110234566 A CN 202110234566A CN 113292819 A CN113292819 A CN 113292819A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 149
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 149
- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 23
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000000945 filler Substances 0.000 claims abstract description 72
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 58
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 25
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 7
- 239000011159 matrix material Substances 0.000 claims description 41
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000005995 Aluminium silicate Substances 0.000 claims description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims description 17
- 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 17
- 238000003756 stirring Methods 0.000 claims description 17
- RYUJRXVZSJCHDZ-UHFFFAOYSA-N 8-methylnonyl diphenyl phosphate Chemical group 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
- LLPKQRMDOFYSGZ-UHFFFAOYSA-N 2,5-dimethyl-1h-imidazole Chemical compound CC1=CN=C(C)N1 LLPKQRMDOFYSGZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims description 10
- 239000010425 asbestos Substances 0.000 claims description 10
- 229910052895 riebeckite Inorganic materials 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000010453 quartz Substances 0.000 claims description 7
- 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 claims description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012779 reinforcing material Substances 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
- 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
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001723 curing Methods 0.000 abstract description 112
- 230000009477 glass transition Effects 0.000 abstract description 11
- 238000013035 low temperature curing Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 description 22
- 239000003365 glass fiber Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 10
- 238000005520 cutting process Methods 0.000 description 9
- 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
- 230000000694 effects Effects 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 6
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000019359 magnesium stearate Nutrition 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
- 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 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
- 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone 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
- 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
- 238000003889 chemical engineering 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
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000004744 fabric Substances 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
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance 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-based 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-based composite material which are cured at medium and low temperatures and the preparation method thereof, the raw materials such as the anhydride curing agent and the imidazole accelerator in the epoxy resin composition are matched, so that the medium and low temperature curing time of the epoxy resin-based composite material can be obviously shortened, 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.
Description
Technical Field
The invention belongs to the technical field of epoxy resin-based composite materials, and particularly relates to a medium-low temperature fast-curing epoxy resin composition, an epoxy resin-based composite material and a preparation method thereof.
Background
Epoxy resin is an advanced composite material resin matrix, and has excellent performance, particularly in wear resistance, mechanical property, adhesion property, chemical stability, electrical insulation property, adhesion property to a base material and the like, so that the figure of the epoxy resin can be seen in the fields of machinery, chemical engineering, buildings, railway traffic, 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 the glass fiber reinforced plastic section bar with unlimited length by molding and curing the continuous fiber bundle, belt or cloth impregnated with the 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 easiness in industrial continuous production, high production efficiency, capability of realizing multi-mould and multi-piece, capability of fully exerting the mechanical property of continuous fibers, stable product performance and the like, and is rapidly developed in recent years. With the development of the composite material pultrusion industry market, the competition in the industry is intensified, and under the situation, the speed is increased and the cost is reduced to become the first choice of various composite material manufacturers.
In the prior art, the epoxy resin matrix material is generally high in viscosity, and when thick-wall products are produced, the conventional method is adopted to improve the pultrusion speed, so that the internal fiber of the products is easily poor in impregnation, the mechanical property of the products is reduced, even the rejection rate is increased, and unnecessary waste is generated; and the epoxy resin matrix material has low glass transition temperature, higher curing temperature and low curing speed at medium and low temperature, so that the production efficiency of the epoxy resin composite material is low.
Disclosure of Invention
The invention solves the technical problem of providing the epoxy resin composition capable of being cured at medium and low temperature quickly, the epoxy resin-based composite material and the preparation method thereof, and the epoxy resin-based composite material can obviously shorten the medium and low temperature curing time of the epoxy resin-based composite material and obviously improve the pultrusion speed of the composite material in the pultrusion process by matching the raw materials such as the anhydride curing agent, the imidazole accelerator and the like in the epoxy resin composition, and the composite material has excellent mechanical property and high glass transition temperature.
In order to solve the above problems, an aspect of the present invention provides a medium-low temperature fast-curing epoxy resin composition, which 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.
The epoxy resin composition capable of being cured at medium and low temperatures quickly is compounded by adopting the imidazole accelerator and the anhydride curing agent, 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 glass transition temperature is higher.
Preferably, the medium-low temperature fast curing epoxy resin composition comprises the following components in parts by mass:
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 is obviously improved, and the internal fiber of the product is high in dipping speed in glue solution, good in dipping effect, optimal in mechanical property and high in vitrification temperature. Within the preferable formula range, the pultrusion speed of the thick-walled product of the epoxy resin composite material can be improved to 0.3m/min, the mechanical property of the product is stable, and no dry yarn exists inside the product; in addition, the glass transition temperature of the product can reach 130 ℃.
Preferably, the acid anhydride curing agent is a low-viscosity acid anhydride curing agent having a viscosity of 100-300mpa.s at 25 ℃. The invention adopts the low-viscosity acid anhydride curing agent, and the low-viscosity acid anhydride curing agent plays a role of a diluent for the epoxy resin composition, and obviously reduces the viscosity of the resin glue solution, so that the fiber dipping speed in the production process can be improved, the pultrusion speed of the composite material in the pultrusion process is improved, and the dipping effect of the composite material is improved.
Preferably, the low-viscosity acid anhydride curing agent is one or a mixture of several of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride.
Preferably, the filler comprises a first filler, a second filler, a third filler, 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 asbestos powder and quartz powder;
the third filler is silica gel powder;
the fourth filler is diphenyl isodecyl phosphate.
In the epoxy resin composition capable of being rapidly cured at medium and low temperatures, various fillers in the fillers and a resin matrix are mainly interacted 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 small 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 stable size of the product interface; the silica gel powder in the filler can better improve the heat resistance of the epoxy resin composite material and positively contributes to the glass transition temperature. Diphenyl isodecyl phosphate in the filler can further improve the flame retardant and toughening effects of the epoxy resin composition.
Preferably, in the fillers, the mass ratio of the first filler to the second filler to the third filler to the fourth filler is 1: (4-5): (3-4): (5-7).
A large number of experimental trials find that when the four fillers in the fillers are selected according to the proportion, the obtained epoxy resin composition has the best mechanical property, the highest impregnation speed, the best impregnation effect, the greatly improved pultrusion rate, the higher medium-low temperature curing speed and the highest glass transition temperature.
Preferably, the imidazole accelerator is one or a mixture of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole and 2, 4-dimethylimidazole.
Preferably, the toughening agent is one or a mixture of several of dioctyl phthalate, dibutyl phthalate, triphenyl phosphate and tricresyl phosphate.
Preferably, the release agent is one or a mixture of barium stearate, calcium stearate, magnesium stearate and zinc stearate.
Another aspect of the present invention provides a method for preparing the above-mentioned medium-low temperature fast-curing epoxy resin composition, comprising the steps of:
and 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 medium-low temperature fast curing epoxy resin composition.
Preferably, the method for preparing the medium-low temperature fast curing epoxy resin composition 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 parts, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20 min;
s2, adding the imidazole promoter and the anhydride curing agent into the product obtained in the step S1, and stirring at the rotation speed of 1000-1500r/min for 10-20min to obtain the medium-low temperature fast curing epoxy resin composition.
Yet another aspect of the present invention provides an epoxy resin-based composite material, comprising:
the epoxy resin composition comprises a resin matrix and a reinforcing material, wherein the resin matrix is the medium-low temperature fast curing epoxy resin composition.
Preferably, the reinforcing material is glass fiber or carbon fiber.
In another aspect, the present invention provides a method for preparing the epoxy resin-based composite material, comprising the following steps:
and impregnating the reinforcing material in the resin matrix, and then molding and curing by adopting a pultrusion process to obtain the epoxy resin-based composite material.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the epoxy resin composition capable of being rapidly cured at the medium and low temperature, 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 and low temperature curing speed of the epoxy resin composition is faster, and the glass transition temperature is higher; the low-viscosity acid anhydride curing agent is adopted, and can play a role of a diluent for the epoxy resin composition due to the low-viscosity curing agent, so that the viscosity of the resin glue solution is obviously reduced, 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 is improved;
2. the formula of the epoxy resin composition capable of being rapidly cured at the medium and low temperature is further optimized, so that the pultrusion speed of the obtained epoxy resin composition in the pultrusion production process is remarkably improved, and the internal fibers of the product are rapidly impregnated in the glue solution, the impregnation effect is good, the mechanical property of the product is optimal, and the vitrification temperature is high. Within the preferable formula range, the pultrusion speed of the thick-walled product of the epoxy resin composite material can be improved to 0.3m/min, the mechanical property of the product is stable, and no dry yarn exists inside the product; in addition, the glass transition temperature of the product can reach 130 ℃.
3. The middle-low temperature fast curing epoxy resin composition provided by the invention has the advantages that various fillers in the fillers and a resin matrix are mainly subjected to physical adsorption, namely, electrostatic force interaction. In the filler, the kaolin and the calcined kaolin can improve the resin content of the product, reduce the production cost and have small 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 stable size of the product interface; the silica gel powder in the filler can better improve the heat resistance of the epoxy resin composite material and positively contributes to the glass transition temperature. 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 described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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
The medium-low temperature fast-curing epoxy resin composition described in this embodiment includes 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 flexibilizer 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 medium-low temperature fast-curing epoxy resin composition of 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 parts, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20 min;
s2, adding an imidazole promoter and an anhydride curing agent into the product obtained in the step S1, and stirring at the rotation speed of 1000-1500r/min for 10-20min to obtain the medium-low temperature fast curing epoxy resin composition.
The epoxy resin-based composite material of the embodiment comprises: 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 number of EDR960-T911, and are purchased from Taishan glass fiber company Limited; the linear density of the product is 2400 plus or minus 120tex, the water content is less than or equal to 0.10 percent, and the combustible content is 0.40 to 0.70 percent.
The preparation method comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a threading drawing, then dipping in the obtained medium-low temperature fast curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, performing preforming, performing extrusion molding and curing → drawing → cutting → preparing, wherein the curing stage adopts zone curing, the front zone curing temperature is 110-; and (3) adopting a reciprocating type pultrusion machine for traction, wherein the pultrusion speed is 0.25m/min, and obtaining the epoxy resin matrix composite material.
Example 2
The medium-low temperature fast-curing epoxy resin composition described in this embodiment includes 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 methyl tetrahydrophthalic anhydride, 10 parts of flexibilizer methyl tetrahydrophthalic anhydride 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 1:4.5:3.5: 6.5.
The preparation method of the medium-low temperature fast-curing epoxy resin composition of 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 parts, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20 min;
s2, adding an imidazole promoter and an anhydride curing agent into the product obtained in the step S1, and stirring at the rotation speed of 1000-1500r/min for 10-20min to obtain the medium-low temperature fast curing epoxy resin composition.
The epoxy resin-based composite material of the embodiment comprises: the obtained epoxy resin composition resin matrix and glass fiber reinforced material with medium and low temperature and fast curing.
The preparation method comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a threading drawing, then dipping in the obtained medium-low temperature fast curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 67%, performing preforming, performing extrusion molding and curing → drawing → cutting → preparing, wherein the curing stage adopts zone curing, the front zone curing temperature is 105-; and (3) adopting a reciprocating type pultrusion machine for traction, wherein the pultrusion speed is 0.27m/min, and obtaining the epoxy resin matrix composite material.
Example 3
The medium-low temperature fast-curing epoxy resin composition described in this embodiment includes 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 flexibilizer 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 in a mass ratio of 1:5:3.5: 6.
The preparation method of the medium-low temperature fast-curing epoxy resin composition of 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 parts, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20 min;
s2, adding an imidazole promoter and an anhydride curing agent into the product obtained in the step S1, and stirring at the rotation speed of 1000-1500r/min for 10-20min to obtain the medium-low temperature fast curing epoxy resin composition.
The epoxy resin-based composite material of the embodiment comprises: the obtained epoxy resin composition resin matrix and glass fiber reinforced material with medium and low temperature and fast curing.
The preparation method comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a threading drawing, then dipping in the obtained medium-low temperature fast curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, performing preforming, performing extrusion molding and curing → drawing → cutting → preparing, wherein the curing stage adopts zone curing, the front zone curing temperature is 110-; and (3) adopting a reciprocating type pultrusion machine for traction, wherein the pultrusion speed is 0.3m/min, and obtaining the epoxy resin matrix composite material.
Example 4
The medium-low temperature fast-curing epoxy resin composition described in this embodiment includes 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 flexibilizer 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 in a mass ratio of 1:4.5:4: 5.5.
The preparation method of the medium-low temperature fast-curing epoxy resin composition of 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 parts, stirring for 20-30min at the rotating speed of 500-800r/min, then increasing the rotating speed to 1000-1500r/min, and stirring for 10-20 min;
s2, adding an imidazole promoter and an anhydride curing agent into the product obtained in the step S1, and stirring at the rotation speed of 1000-1500r/min for 10-20min to obtain the medium-low temperature fast curing epoxy resin composition.
The epoxy resin-based composite material of the embodiment comprises: the obtained epoxy resin composition resin matrix and glass fiber reinforced material with medium and low temperature and fast curing.
The preparation method comprises the following steps:
reasonably arranging glass fiber reinforced materials according to a threading drawing, then dipping in the obtained medium-low temperature rapidly cured epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, performing preforming, performing extrusion molding and curing → drawing → cutting → preparing, wherein the curing stage adopts zone curing, the front zone curing temperature is 105-; and (3) adopting a reciprocating type pultrusion machine for traction, wherein the pultrusion speed is 0.3m/min, and obtaining the epoxy resin matrix composite material.
Example 5
The medium-low temperature fast-curing epoxy resin composition described in this embodiment includes 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 in a mass ratio of 1:4.5:3: 6.
The preparation method of the medium and low temperature fast curing epoxy resin composition of this example is the same as that of 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 threading drawing, then dipping in the obtained medium-low temperature fast curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 67%, performing preforming, performing extrusion molding and curing → drawing → cutting → preparing, wherein the curing stage adopts zone curing, the front zone curing temperature is 100-; and (3) adopting a reciprocating type pultrusion machine for traction, wherein the pultrusion speed is 0.2m/min, and obtaining the epoxy resin matrix composite material.
Example 6
The medium-low temperature fast-curing epoxy resin composition described in this embodiment includes 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 flexibilizer 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 according to the mass ratio of 1:4.5:3.5: 6.5.
The preparation method of the medium and low temperature fast curing epoxy resin composition of this example is the same as that of 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 threading drawing, then dipping in the obtained medium-low temperature fast curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, performing preforming, performing extrusion molding and curing → drawing → cutting → preparing, wherein the curing stage adopts zone curing, the front zone curing temperature is 110-; and (3) adopting a reciprocating type pultrusion machine for traction, wherein the pultrusion speed is 0.27m/min, and obtaining the epoxy resin matrix composite material.
Example 7
The medium-low temperature fast-curing epoxy resin composition described in this embodiment includes 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 methyl tetrahydrophthalic anhydride, 1 part of flexibilizer 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 preparation method of the medium and low temperature fast curing epoxy resin composition of this example is the same as that of 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 threading drawing, then dipping in the obtained medium-low temperature rapidly cured epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 65%, performing preforming, performing extrusion molding and curing → drawing → cutting → preparing, wherein the curing stage adopts zone curing, the front zone curing temperature is 130-; and (3) adopting a reciprocating type pultrusion machine for traction, wherein the pultrusion speed is 0.15m/min, and obtaining the epoxy resin matrix composite material.
Example 8
The medium-low temperature fast-curing epoxy resin composition described in this embodiment includes 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 methyl tetrahydrophthalic 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 in a mass ratio of 1:4.5:3: 5.5.
The preparation method of the medium and low temperature fast curing epoxy resin composition of this example is the same as that of 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 threading drawing, then dipping in the obtained medium-low temperature fast curing epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 67%, performing preforming, performing extrusion molding and curing → drawing → cutting → preparing, wherein the curing stage adopts zone curing, the front zone curing temperature is 130-; and (3) adopting a reciprocating type pultrusion machine to pull, wherein the pultrusion speed is 0.12m/min to obtain the epoxy resin-based composite material.
Comparative example
The epoxy resin composition of this comparative example includes 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 epoxy resin composition of this comparative example was prepared in the same manner as in example 1.
The preparation method of the epoxy resin-based composite material comprises the following steps:
arranging glass fiber reinforced materials reasonably according to a threading drawing, then dipping in the obtained epoxy resin composition resin matrix, wherein the volume fraction of the resin matrix after dipping is 70%, performing preforming, and performing extrusion molding, curing → traction → cutting → products, wherein the curing stage adopts zone curing, the front zone curing temperature is 140-; and (3) adopting a reciprocating type pultrusion machine for traction, wherein the pultrusion 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 above examples and comparative examples were measured, and the measurement results are shown in table 1 below.
TABLE 1
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The medium-low temperature fast curing epoxy resin composition is characterized by comprising 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.
2. The medium-low temperature fast curing epoxy resin composition as claimed in claim 1, wherein the medium-low temperature fast curing epoxy resin composition comprises the following components in parts by mass:
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.
3. The medium to low temperature fast curing epoxy resin composition according to claim 1, characterized in that:
the acid anhydride curing agent is a low-viscosity acid anhydride curing agent, and the viscosity of the low-viscosity acid anhydride curing agent at 25 ℃ is 100-300 mPa.s.
4. The medium to low temperature fast curing epoxy resin composition according to claim 3, characterized in that:
the low-viscosity acid anhydride curing agent is one or a mixture of several of tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methylnadic anhydride.
5. The medium to low temperature fast curing epoxy resin composition according to claim 1, characterized in that:
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 asbestos powder and quartz powder;
the third filler is silica gel powder;
the fourth filler is diphenyl isodecyl phosphate.
6. The medium to low temperature fast curing epoxy resin composition according to claim 1, characterized in that:
in the fillers, 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).
7. The medium to low temperature fast curing epoxy resin composition according to claim 1, characterized in that:
the imidazole accelerator is one or a mixture of more of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole and 2, 4-dimethylimidazole.
8. A process for preparing the medium-low temperature fast-curing epoxy resin composition as claimed in any one of claims 1 to 7, comprising the steps of:
and 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 medium-low temperature fast curing epoxy resin composition.
9. An epoxy resin-based composite material, comprising:
a resin matrix and a reinforcing material, wherein the resin matrix is the medium-low temperature fast curing epoxy resin composition as claimed in any one of claims 1 to 7.
10. A method for preparing the epoxy resin-based composite material according to claim 9, comprising the steps of:
and impregnating the reinforcing material in the resin matrix, and then molding and curing by adopting a pultrusion process to obtain the epoxy resin-based composite material.
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| CN114891317A (en) * | 2022-05-16 | 2022-08-12 | 上纬新材料科技股份有限公司 | Degradable pultruded panel composite material and application thereof to wind power blade |
| CN114891317B (en) * | 2022-05-16 | 2023-12-26 | 上纬新材料科技股份有限公司 | Degradable pultrusion plate composite material and application thereof on wind power blade |
| CN115232442A (en) * | 2022-08-02 | 2022-10-25 | 惠柏新材料科技（上海）股份有限公司 | Epoxy resin composition and preparation method and application thereof |
| CN115058099A (en) * | 2022-08-18 | 2022-09-16 | 北京玻钢院复合材料有限公司 | Epoxy resin composition with two-phase sea-island structure, composite material and preparation method thereof |
| CN115058099B (en) * | 2022-08-18 | 2022-11-11 | 北京玻钢院复合材料有限公司 | Epoxy resin composition with two-phase sea-island structure, composite material and preparation method of epoxy resin composition |
| WO2024037194A1 (en) * | 2022-08-18 | 2024-02-22 | 北京玻钢院复合材料有限公司 | Epoxy resin composition having two-phase sea-island structure, composite material, and preparation methods therefor |
| CN115960337A (en) * | 2023-02-17 | 2023-04-14 | 南京海拓复合材料有限责任公司 | Epoxy resin curing agent for pultrusion of composite material and preparation method thereof |
| CN115960337B (en) * | 2023-02-17 | 2023-12-26 | 南京海拓复合材料有限责任公司 | Epoxy resin curing agent for composite material pultrusion and preparation method thereof |
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