CN114163670A - Energy-saving and environment-friendly epoxy vinyl ester resin prepreg and preparation method and curing method thereof - Google Patents
Energy-saving and environment-friendly epoxy vinyl ester resin prepreg and preparation method and curing method thereof Download PDFInfo
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- CN114163670A CN114163670A CN202111356095.7A CN202111356095A CN114163670A CN 114163670 A CN114163670 A CN 114163670A CN 202111356095 A CN202111356095 A CN 202111356095A CN 114163670 A CN114163670 A CN 114163670A
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- prepreg
- vinyl ester
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- epoxy vinyl
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- 229920006241 epoxy vinyl ester resin Polymers 0.000 title claims abstract description 30
- 238000001723 curing Methods 0.000 title abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000004641 Diallyl-phthalate Substances 0.000 claims abstract description 11
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 10
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 239000004744 fabric Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 10
- 238000003892 spreading Methods 0.000 claims description 10
- 230000007480 spreading Effects 0.000 claims description 10
- 239000003365 glass fiber Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 claims description 6
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- IFXDUNDBQDXPQZ-UHFFFAOYSA-N 2-methylbutan-2-yl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CC IFXDUNDBQDXPQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 238000004806 packaging method and process Methods 0.000 claims description 5
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 claims description 4
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 claims description 3
- ZTFSXSAVDJCOLB-UHFFFAOYSA-N 2-ethylhexanoyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(=O)C(CC)CCCC ZTFSXSAVDJCOLB-UHFFFAOYSA-N 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000004698 Polyethylene Substances 0.000 description 11
- -1 polyethylene Polymers 0.000 description 11
- 229920000573 polyethylene Polymers 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000002955 isolation Methods 0.000 description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005057 refrigeration Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000008719 thickening Effects 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PQTFPUORFUNSDH-UHFFFAOYSA-N ethyl hexaneperoxoate Chemical compound CCCCCC(=O)OOCC PQTFPUORFUNSDH-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
- C08J2363/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides an epoxy vinyl ester resin prepreg, a preparation method and a curing method thereof, wherein the prepreg comprises resin and reinforcing fibers, the resin comprises 55-70% of epoxy vinyl ester, 20-38% of normal temperature crystallization monomer, 5-10% of vinyl monomer and 0.5-2% of curing agent by mass percent of 100%, and the preparation method comprises the steps of heating the epoxy vinyl ester, adding diallyl phthalate, stirring while keeping the temperature, adding the normal temperature crystallization monomer, continuing stirring while keeping the temperature, then cooling, adding the curing agent, and stirring while keeping the temperature to obtain the resin. Heating the resin to enable the resin to enter a molten state, immersing the reinforcing fibers into the resin in the molten state, and extruding redundant resin to obtain the prepreg. The prepreg disclosed by the invention is milder in curing temperature and conditions, and is more energy-saving and environment-friendly when applied to industrial production.
Description
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to an energy-saving and environment-friendly epoxy vinyl ester resin prepreg and a preparation method and a curing method thereof.
Background
The composite material manufactured by the continuous fiber prepreg has the advantages of high mechanical property, good consistency, sanitary working environment and the like, and is widely applied to the high and new technical fields of aerospace and the like. With the development of advanced equipment in the civil and military field in China, particularly the popularization and application of high-performance composite materials on large-scale equipment such as ships, rail transit and the like, the demand on the high-performance composite materials is more and more increased, the continuous fiber prepreg is mainly developed for aerospace equipment at present, the manufactured composite material member has excellent mechanical property, but the prepreg has high cost, needs high-temperature curing, has low curing speed and needs special equipment for curing, and is not suitable for manufacturing the large-scale equipment such as the ships, the rail transit and the like. Therefore, in order to enable the prepreg to be suitable for production of large civil components, a crosslinking monomer is introduced in the prior art, and the curing temperature is reduced in a free radical initiated curing mode, so that the prepreg is well popularized.
The currently commonly used crosslinking monomer is mainly styrene or methyl methacrylate, and the two monomers have higher volatility on one hand, so that the production process is not environment-friendly enough; on the other hand, the vinyl ester resin diluted by the two monomers needs to be thickened by chemical thickeners such as MgO, CaO, inorganic thixotropic agents or isocyanate, on one hand, the thickeners can reduce the mechanical property of a large complex structure prepared by the prepreg to a certain extent, on the other hand, the resin components in the prepreg still have high viscosity at the molding temperature (below 100 ℃), and the prepreg needs to be filled with a mold under the conditions of high temperature and high pressure, so that the prepreg is not suitable for a vacuum bag pressing process with low cost, and the difficulty and the cost of production and processing are greatly improved.
Disclosure of Invention
In view of the above, the invention provides an epoxy vinyl ester resin prepreg, a preparation method thereof and a curing method thereof, wherein the epoxy vinyl ester resin prepreg can effectively reduce the curing temperature of the prepreg, can improve the environmental protection performance of the prepreg in the production and processing processes to a certain extent, and can improve the mechanical performance of the prepreg after curing.
The technical scheme of the invention is realized as follows: the invention provides an energy-saving environment-friendly epoxy vinyl ester resin prepreg, which comprises resin and reinforcing fiber, wherein the resin comprises the following components in percentage by mass of 100 percent:
on the basis of the technical scheme, preferably, the energy-saving environment-friendly epoxy vinyl ester resin prepreg comprises 25-50% of resin and 50-75% of reinforcing fiber according to the mass percentage of 100%.
On the basis of the technical scheme, preferably, the normal-temperature crystallization monomer is one or more of N-methylmaleimide, N-cyclohexylmaleimide, tetrahydrophthalic anhydride and maleic anhydride.
Based on the above technical solution, preferably, the vinyl monomer is diallyl phthalate.
On the basis of the technical scheme, preferably, the diallyl phthalate is one or more of diallyl phthalate, diallyl isophthalate and diallyl terephthalate.
More preferably, the curing agent is one of 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxide) hexane, tert-butyl peroxy-2-ethylhexanoate and tert-amyl peroxy-2-ethylhexanoate.
On the basis of the above technical solution, preferably, the reinforcing fiber is one of a glass fiber, a glass fiber fabric, a carbon fiber and a carbon fiber fabric.
The invention also provides a preparation method of the energy-saving environment-friendly epoxy vinyl ester resin prepreg, which comprises the following steps:
step S1, heating epoxy vinyl ester to 60-80 ℃, adding diallyl phthalate, stirring for 20-40min under heat preservation, adding a normal-temperature crystallization monomer, continuing stirring for 40-80min under heat preservation, cooling to 45-55 ℃, adding a curing agent, and stirring for 5-15min under heat preservation to obtain resin;
and step S2, heating the resin to be in a molten state, immersing the reinforcing fibers into the molten resin, extruding redundant resin to obtain a prepreg, covering films on the upper surface and the lower surface of the prepreg, coiling and packaging, and storing at the temperature of-20 to-10 ℃.
In addition to the above technical solutions, the films covered on the upper and lower surfaces of the prepreg may be preferably polyethylene films or release paper, and most preferably, one side surface is covered with a polyethylene film, and the other side surface is covered with release paper.
The invention also provides a curing method of the energy-saving environment-friendly epoxy vinyl ester resin prepreg, which specifically comprises the following steps:
firstly, tearing off a film on one surface of a prepreg, paving the film on the surface of a mold and tightly attaching the film, then tearing off a film on the other surface of the prepreg, and selectively repeating the steps on the surface of the first layer of the prepreg according to the design thickness of a product to lay the prepreg until the product thickness requirement is met;
then, sequentially paving demoulding cloth, an isolating film and a glue absorption felt on one surface of the prepreg away from the mould from inside to outside, sealing the prepreg forming area by using a vacuum bag, and keeping the vacuum pressure in the vacuum bag to be not lower than-0.08 MPa;
finally, the temperature of the prepreg was raised to 95-100 ℃, the temperature was maintained, and the curing time was determined according to the thickness of the prepreg at 10 min/mm.
On the basis of the above technical scheme, preferably, the method for raising the temperature of the prepreg to 95-100 ℃ comprises the following steps: and (2) introducing a heating medium with the temperature of 95-100 ℃ into the mold, or putting the prepreg and the mold into a heating container together to heat to the temperature of 95-100 ℃.
Compared with the prior art, the energy-saving environment-friendly epoxy vinyl ester resin prepreg, the preparation method and the curing method thereof have the following beneficial effects:
(1) according to the invention, the crystalline crosslinking monomer and the low-volatility crosslinking monomer are reasonably matched with the epoxy vinyl ester resin, the prepreg resin is cured by the curing agent which initiates peroxide curing at low temperature, the obtained prepreg can be formed by vacuum bag pressing, the curing temperature is reduced to 95-100 ℃, the curing time is greatly shortened, the production of enterprises is facilitated, the production conditions are milder compared with the prior art, the dependence on large-scale special equipment is reduced, and the large-scale production of the enterprises is facilitated;
(2) the preparation method and the curing method are simple, the production cost is lower, the operation and condition control are easy, the epoxy vinyl ester resin thickened by the crystalline crosslinking monomer is adopted to replace the traditional alkali metal oxide, inorganic thixotropic agent or isocyanate, and compared with the traditional thickening system, the high-temperature and high-pressure thickening system firstly needs high temperature and high pressure to reduce the viscosity of the resin and effectively fill the mold, the prepreg prepared by the method has the requirement of good spreadability on viscosity at normal temperature, the viscosity of the resin is quickly reduced and the mold is effectively filled at 100 ℃, and the composite material with excellent performance can be obtained only by a simple vacuum bag pressing process, so the manufacturing cost of a large-scale complex high-performance composite material member is greatly reduced;
(3) meanwhile, the invention adopts the crystalline crosslinking monomer and part of the low-volatile crosslinking monomer, and endows the prepreg with the characteristics of no obvious smell and environmental friendliness in the forming process, so that the prepreg has higher performance, lower cost and more environmental protection compared with the prior art.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The scheme of the invention is further illustrated by the following examples:
in the following embodiments:
epoxy vinyl esters are available from Rongwei 901 epoxy vinyl ester resins;
n-methylmaleimide is purchased from Hubei Yunmu technology;
n-cyclohexylmaleimide was purchased from Wuhankangqiong biopharmaceuticals;
tetrahydrophthalic anhydride was purchased from Hubei Jiujiu Fenglong chemical;
maleic anhydride was purchased from Shandong Longhui chemical;
diallyl phthalate was purchased from Shandong Luyuan;
the 2, 5-dimethyl-2, 5-di (2-ethyl hexanoyl peroxide) hexane is purchased from Hubei Hongxin Ruiyu fine chemical industry;
the tert-butyl peroxy-2-ethylhexanoate is purchased from a Zibos-n-Hua auxiliary agent;
the tert-amyl peroxy-2-ethylhexanoate is purchased from a zibo Zhenghua assistant;
example 1
Weighing 11kg of epoxy vinyl ester, heating to 60 ℃, adding 1kg of diallyl phthalate, keeping the temperature and stirring for 20min, weighing 7.6kg of N-methylmaleimide, adding the N-methylmaleimide into the reaction system, keeping the temperature and stirring for 40min, completely dissolving the N-methylmaleimide, cooling the system to 45 ℃, adding 400g of 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxide) hexane, and stirring for 5min at 45 ℃ to obtain the resin.
The method comprises the steps of enabling high-strength glass fiber yarns to enter epoxy vinyl resin in a molten state through a yarn spreader under certain tension to obtain directionally-arranged limiting prepreg, extruding redundant epoxy vinyl ester resin through a glue extruding device, controlling the content of a resin matrix to be 25%, covering a polyethylene film and fluorine-containing release paper on the upper surface and the lower surface respectively, packaging in an aluminum-plated plastic bag after being rolled, boxing, and sending into a refrigeration house at the temperature of-20 to-10 ℃ for storage.
Example 2
Weighing 14kg of epoxy vinyl ester, heating to 60 ℃, adding 1.8kg of diallyl isophthalate, keeping the temperature and stirring for 30min, weighing 4kg of N-cyclohexyl maleimide, adding the N-cyclohexyl maleimide into a reaction system, keeping the temperature and stirring for 60min, completely dissolving the N-cyclohexyl maleimide, cooling the system to 50 ℃, adding 200g of tert-butyl peroxy-2-ethylhexanoate, and keeping the temperature and stirring for 10min to obtain the resin.
The high-strength glass fiber cloth is fed into epoxy vinyl ester resin in a molten state under the assistance of a guide roller, reinforced impregnation is carried out through a heating roller, redundant epoxy vinyl ester resin is extruded out, the content of a resin matrix is controlled to be 50%, the upper surface and the lower surface of the resin matrix are respectively covered with a polyethylene film and fluorine-containing release paper, the resin matrix is packaged into an aluminized plastic bag after being coiled, and the aluminized plastic bag is boxed and sent into a refrigeration house at the temperature of minus 20 ℃ to minus 10 ℃ for storage.
Example 3
Weighing 13kg of epoxy vinyl ester, heating to 70 ℃, adding 2kg of diallyl terephthalate, stirring for 40min under heat preservation, weighing 5.9kg of tetrahydrophthalic anhydride, adding into the reaction system, continuing stirring for 80min under heat preservation, completely dissolving the tetrahydrophthalic anhydride, cooling the system to 55 ℃, adding 100g of tert-amyl peroxy-2-ethylhexanoate, and stirring for 15min under the condition of keeping 55 ℃ to obtain the resin.
The method comprises the steps of enabling T700 carbon fiber yarns to enter epoxy vinyl ester resin in a molten state through a yarn spreader under certain tension to obtain directionally-arranged fiber prepreg, extruding redundant epoxy vinyl ester resin through a glue extruding device, controlling the content of a resin matrix to be 25%, covering polyethylene films and fluorine-containing release paper on the upper surface and the lower surface respectively, packaging the resin prepreg in an aluminum-plated plastic bag after being rolled, boxing the resin in the aluminum-plated plastic bag, and sending the aluminum-plated plastic bag into a refrigeration house at the temperature of-20 to-10 ℃ for storage.
Example 4
Heating 12kg of epoxy vinyl ester to 80 ℃, adding 1.2kg of diallyl terephthalate, stirring for 40min under heat preservation, weighing 6.4kg of maleic anhydride, adding into a reaction system, continuing stirring for 60min under heat preservation, completely dissolving the maleic anhydride, cooling the system to 50 ℃, adding 400g of tert-amyl peroxy-2-ethylhexanoate, and stirring for 10min under the condition of keeping the temperature at 50 ℃ to obtain the resin.
The method comprises the steps of putting T700 carbon fiber cloth into epoxy vinyl ester resin in a molten state with the aid of a guide roller, carrying out reinforced impregnation through a heating roller, extruding redundant epoxy vinyl ester resin, controlling the content of a resin matrix to be 50%, covering polyethylene films and fluorine-containing release paper on the upper surface and the lower surface respectively, packaging the resin matrix in an aluminized plastic bag after being coiled, and conveying the resin matrix into a refrigeration house at the temperature of-20 to-10 ℃ for storage.
In examples 1 to 4, the high strength glass fiber yarn, the high strength glass fiber cloth, and the T700 carbon fiber cloth were stacked in a multi-layer manner, and the laying directions were kept uniform.
Example 5
Tearing the release paper on the surface of the prepreg prepared in the embodiment 1, then spreading the release paper in a mold to ensure that the prepreg is attached to the surface of the mold, tearing the polyethylene film, then removing a second piece of prepreg, tearing the release paper, spreading the release paper on the first layer of prepreg, attaching the first layer of prepreg with the prepreg, repeating the steps until the designed thickness is reached, spreading demolding cloth, an isolation film and an adhesive absorption felt on the surface of the prepreg, sealing a prepreg forming area by using a vacuum bag, vacuumizing until the pressure is-0.09 MPa, introducing circulating water at 98-100 ℃ into the mold, wherein the thickness of the prepreg in the mold is 2mm, so that the curing time is 20min, and demolding after the curing is finished to obtain a prepreg product.
Example 6
Tearing the release paper on the surface of the prepreg prepared in the embodiment 2, spreading the release paper in a mold to ensure that the prepreg is attached to the surface of the mold, tearing the polyethylene film, removing a second piece of prepreg, tearing the release paper, spreading the release paper on the first layer of prepreg, attaching the first layer of prepreg to the first layer of prepreg, repeating the steps until the designed thickness is reached, spreading demolding cloth, an isolation film and an adhesive absorption felt on the surface of the prepreg, sealing a prepreg forming area by using a vacuum bag, vacuumizing until the pressure is-0.09 MPa, introducing circulating water at 98-100 ℃ into the mold, wherein the thickness of the prepreg in the mold is 2mm, so that the curing time is 20min, and demolding to obtain a prepreg product after the curing is finished.
Example 7
Tearing the release paper on the surface of the prepreg prepared in the embodiment 3, paving the release paper in a mold to ensure that the prepreg is attached to the surface of the mold, tearing the polyethylene film, removing a second piece of prepreg, tearing the release paper, paving the release paper on the first layer of prepreg, attaching the first layer of prepreg to the first layer of prepreg, repeating the steps until the designed thickness is reached, paving demolding cloth, an isolation film and an adhesive absorption felt on the surface of the prepreg, sealing the prepreg forming area by using a vacuum bag, vacuumizing until the pressure is-0.09 MPa, putting the prepreg communicated with the mold into an oven, controlling the temperature in the oven to be 95-100 ℃, controlling the thickness of the prepreg in the mold to be 2mm, so that the curing time is 20min, and demolding to obtain a prepreg product after the curing is finished.
Example 8
Tearing the release paper on the surface of the prepreg prepared in the embodiment 4, spreading the release paper in a mold to ensure that the prepreg is attached to the surface of the mold, tearing the polyethylene film, removing a second piece of prepreg, tearing the release paper, spreading the release paper on the first layer of prepreg, attaching the first layer of prepreg to the first layer of prepreg, repeating the steps until the designed thickness is reached, spreading release cloth, an isolation film and an adhesive absorption felt on the surface of the prepreg, sealing the prepreg forming area by using a vacuum bag, vacuumizing to-0.09 MPa, putting the prepreg communicated with the mold into an oven, controlling the temperature in the oven to be 95-100 ℃, controlling the thickness of the prepreg in the mold to be 2mm, so that the curing time is 20min, and demolding to obtain a prepreg product after the curing is finished.
The prepreg products prepared in the above examples 5 to 8 have flat and smooth surfaces, stable forms and properties meeting the requirements of cured products.
Comparative example
Purchasing a commercially available prepreg, tearing release paper on the surface of the prepreg, then paving the prepreg in a mold, ensuring that the prepreg is attached to the surface of the mold, tearing a polyethylene film, then removing a second piece of prepreg, tearing the release paper, paving the first layer of prepreg, attaching the first layer of prepreg and the second layer of prepreg to the first layer of prepreg, repeating the steps until the designed thickness is reached, paving demolding cloth, an isolation film and a glue absorption felt on the surface of the prepreg, sealing a prepreg forming area by using a vacuum bag, vacuumizing until the pressure is-0.09 MPa, putting the prepreg communicated with the mold into an oven, wherein the temperature in the oven is 95-100 ℃, and the prepreg is 2mm thick in the mold, so that the curing time is 20min, demolding to obtain a prepreg product after the curing is finished, and the obtained product is not completely formed and can not reach the curing effect.
The prepreg products prepared in examples 5 to 8 and comparative example were subjected to mechanical property testing, the testing equipment was a 100 kn universal mechanical testing machine, the testing items included that the tensile strength, tensile modulus, compressive strength, compressive modulus, flexural strength, flexural modulus and interlaminar shear strength of the prepreg products were measured, the directions of measurement of the tensile strength, tensile modulus, compressive strength, compressive modulus, flexural modulus and flexural strength were all radial directions of the corresponding fiber layer, the sizes of the sheets for testing were unified to be 250mm in length, 25mm in width and 2mm in thickness, and the results of the tests were as follows:
the results of the above examples and comparative examples show that, by using the prepreg of the present invention, curing can be completed in a relatively short time under a temperature condition of less than 100 ℃, and the cured product has good performance, while under the same conditions, the comparative example cannot complete curing, and finally the obtained product cannot be tested for partial mechanical properties.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The energy-saving and environment-friendly epoxy vinyl ester resin prepreg is characterized by comprising resin and reinforcing fibers, wherein the resin comprises the following components in percentage by mass of 100 percent:
2. the energy-saving environment-friendly epoxy vinyl ester resin prepreg according to claim 1, wherein the normal temperature crystallization monomer is one or more of N-methyl maleimide, N-cyclohexyl maleimide, tetrahydrophthalic anhydride and maleic anhydride.
3. The energy efficient, environmentally friendly epoxy vinyl ester resin prepreg of claim 1, wherein the vinyl monomer is diallyl phthalate.
4. The energy-saving environment-friendly epoxy vinyl ester resin prepreg according to claim 3, wherein the diallyl phthalate is one or more of diallyl phthalate, diallyl isophthalate and diallyl terephthalate.
5. The energy-saving environment-friendly epoxy vinyl ester resin prepreg according to claim 1, wherein the curing agent is one of 2, 5-dimethyl-2, 5-di (2-ethylhexanoylperoxide) hexane, t-butyl peroxy-2-ethylhexanoate and t-amyl peroxy-2-ethylhexanoate.
6. The energy efficient and environmentally friendly epoxy vinyl ester resin prepreg of claim 1, wherein the reinforcing fiber is one of a glass fiber, a glass fiber fabric, a carbon fiber and a carbon fiber fabric.
7. The method for preparing the energy-saving and environment-friendly epoxy vinyl ester resin prepreg according to any one of claims 1 to 6, which is characterized by comprising the following steps:
step S1, heating epoxy vinyl ester to 60-80 ℃, adding diallyl phthalate, stirring for 20-40min under heat preservation, adding a normal-temperature crystallization monomer, continuing stirring for 40-80min under heat preservation, cooling to 45-55 ℃, adding a curing agent, and stirring for 5-15min under heat preservation to obtain resin;
and step S2, heating the resin to be in a molten state, immersing the reinforcing fibers into the molten resin, extruding redundant resin to obtain a prepreg, covering films on the upper surface and the lower surface of the prepreg, coiling and packaging, and storing at the temperature of-20 to-10 ℃.
8. The method for curing an energy efficient and environmentally friendly epoxy vinyl ester resin prepreg according to any one of claims 1 to 6, comprising:
tearing off the film on one surface of the prepreg, spreading the film on the surface of the mold and tightly attaching the film, then tearing off the film on the other surface, and selectively repeating the steps on the surface of the first layer of prepreg according to the design thickness of the product to lay the prepreg until the product thickness requirement is met;
sequentially paving demolding cloth, an isolating film and a glue absorption felt on one surface of the prepreg far away from the mold from inside to outside, sealing a prepreg forming area by using a vacuum bag, and then keeping the vacuum pressure in the vacuum bag to be not lower than-0.08 MPa;
the temperature of the prepreg was raised to 95-100 ℃, the temperature was maintained, and the curing time was determined according to the thickness of the prepreg at 10 min/mm.
9. The method of curing an energy efficient and environmentally friendly epoxy vinyl ester resin prepreg according to claim 8, wherein the step of raising the temperature of the prepreg to 95-100 ℃ comprises: and (2) introducing a heating medium with the temperature of 95-100 ℃ into the mold, or putting the prepreg and the mold into a heating container together and heating to the temperature of 95-100 ℃.
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