CN114163670B - Energy-saving environment-friendly epoxy vinyl ester resin prepreg, and preparation method and curing method thereof - Google Patents
Energy-saving environment-friendly epoxy vinyl ester resin prepreg, and preparation method and curing method thereof Download PDFInfo
- Publication number
- CN114163670B CN114163670B CN202111356095.7A CN202111356095A CN114163670B CN 114163670 B CN114163670 B CN 114163670B CN 202111356095 A CN202111356095 A CN 202111356095A CN 114163670 B CN114163670 B CN 114163670B
- Authority
- CN
- China
- Prior art keywords
- prepreg
- resin
- vinyl ester
- epoxy vinyl
- curing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920006241 epoxy vinyl ester resin Polymers 0.000 title claims abstract description 26
- 238000001723 curing Methods 0.000 title abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000004641 Diallyl-phthalate Substances 0.000 claims abstract description 11
- 239000004593 Epoxy 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
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000012783 reinforcing fiber Substances 0.000 claims abstract description 7
- 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 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000004744 fabric Substances 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 238000013461 design Methods 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000465 moulding Methods 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- 239000003292 glue Substances 0.000 claims description 6
- 238000000926 separation method Methods 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
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-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
- 230000007613 environmental effect Effects 0.000 claims description 4
- WYKYCHHWIJXDAO-UHFFFAOYSA-N tert-butyl 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)C WYKYCHHWIJXDAO-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
- 238000003892 spreading Methods 0.000 claims description 2
- 230000007480 spreading Effects 0.000 claims description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- -1 polyethylene Polymers 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 7
- 238000004132 cross linking Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000012545 processing Methods 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000013329 compounding Methods 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
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005502 peroxidation 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
- 238000005057 refrigeration Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005303 weighing Methods 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The application 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 crystalline monomer, 5-10% of vinyl monomer and 0.5-2% of curing agent by mass percent, and the preparation method comprises the steps of heating the epoxy vinyl ester, adding diallyl phthalate, carrying out heat preservation and stirring, adding the normal-temperature crystalline monomer, continuing to carry out heat preservation and stirring, then cooling, adding the curing agent, carrying out heat preservation and stirring, and obtaining the resin. Heating resin to make it into molten state, immersing reinforcing fiber into molten resin, extruding excess resin to obtain prepreg, and said solidifying method includes such steps as laying prepreg in mould, laying multiple layers, and heating under negative pressure to solidify. The curing temperature and the curing conditions of the prepreg are milder, and the prepreg is more energy-saving and environment-friendly when applied to industrial production.
Description
Technical Field
The application relates to the technical field of polymer composite materials, in particular to an energy-saving and environment-friendly epoxy vinyl ester resin prepreg, 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. Along with the development of advanced equipment in the field of military and civil engineering 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 for the high-performance composite materials is increased, the continuous fiber prepreg is mainly developed for aerospace equipment at present, the mechanical properties of manufactured composite material components are excellent, but the prepreg is high in cost, needs high-temperature curing, is slow in curing speed, needs special equipment for curing, and is not suitable for manufacturing large-scale equipment such as ships, rail transit and the like. Therefore, in order to enable the prepreg to be suitable for the production of large civil components, the prior art introduces a crosslinking monomer, and reduces the curing temperature in a free radical initiated curing mode, so that the prepreg is well popularized.
The crosslinking monomers commonly used at present are mainly styrene or methyl methacrylate, and the two monomers have larger volatility on one hand, so that the production process is not environment-friendly; 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, and the like, and the thickeners can reduce the mechanical properties of a large complex structure prepared by the prepreg to a certain extent, and on the other hand, the resin component in the prepreg still has high viscosity at the molding temperature (below 100 ℃), the resin component needs to be subjected to mold filling under the high-temperature and high-pressure conditions, and the resin is not suitable for a vacuum bagging process with low cost, so that the difficulty and cost of production and processing are greatly improved.
Disclosure of Invention
In view of the above, the application provides an epoxy vinyl ester resin prepreg which can effectively reduce the curing temperature of the prepreg, and can improve the environmental protection performance of the prepreg in the production and processing processes to a certain extent and improve the mechanical performance of the cured prepreg, and a preparation method and a curing method thereof.
The technical scheme of the application is realized as follows: the application provides an energy-saving environment-friendly epoxy vinyl ester resin prepreg which comprises resin and reinforcing fibers, wherein the resin comprises the following components in percentage by mass as 100 percent:
on the basis of the technical scheme, preferably, the energy-saving and environment-friendly epoxy vinyl ester resin prepreg comprises 25-50% of resin and 50-75% of reinforcing fibers according to the mass percentage of 100%.
On the basis of the technical scheme, the normal-temperature crystallization monomer is preferably one or more of N-methyl maleimide, N-cyclohexyl maleimide, tetrahydrophthalic anhydride and maleic anhydride.
In 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.
Still more preferably, the curing agent is one of 2, 5-dimethyl-2, 5-di (2-ethylhexanoyl peroxide) hexane, tert-butyl peroxy-2-ethylhexanoate, tert-amyl peroxy-2-ethylhexanoate.
On the basis of the technical scheme, preferably, the reinforcing fiber is one of glass fiber, glass fiber fabric, carbon fiber and carbon fiber fabric.
The application 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, carrying out heat preservation and stirring for 20-40min, adding normal-temperature crystallization monomers, continuing to carry out heat preservation and stirring for 40-80min, cooling to 45-55 ℃, adding a curing agent, and carrying out heat preservation and stirring for 5-15min to obtain resin;
and S2, heating the resin to enable the resin to enter a molten state, immersing the reinforced fiber into the resin in the molten state, extruding the redundant resin to obtain the prepreg, covering films on the upper surface and the lower surface of the prepreg, coiling and packaging, and then storing at the temperature of-20 to-10 ℃.
On the basis of the technical scheme, the films covered on the upper surface and the lower surface of the prepreg can be polyethylene films or release papers, and the most preferable is that one side surface is covered with the polyethylene films and the other side surface is covered with the release papers.
The application also provides a curing method of the energy-saving environment-friendly epoxy vinyl ester resin prepreg, which comprises the following steps:
firstly, tearing a film on one side of the prepreg, paving the film on the surface of a die, closely attaching the film, tearing the film on the other side, and selectively repeating the steps on the surface of the first layer of prepreg according to the design thickness of a product until the thickness requirement of the product is met;
then, spreading release cloth, a separation film and a glue absorbing felt on one surface of the prepreg far away from the die in sequence from inside to outside, sealing the prepreg molding area by using a vacuum bag, and keeping the vacuum pressure in the vacuum bag at least below-0.08 MPa;
finally, the temperature of the prepreg was raised to 95-100℃and 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 solution, preferably, the method for raising the temperature of the prepreg to 95-100 ℃ includes: and (3) introducing a heating medium at 95-100 ℃ into the mold, or placing the prepreg together with the mold into a heating container to heat to 95-100 ℃.
Compared with the prior art, the energy-saving environment-friendly epoxy vinyl ester resin prepreg and the preparation method and the curing method thereof have the following beneficial effects:
(1) The application adopts the reasonable matching of the crystalline crosslinking monomer and the low-volatility crosslinking monomer with the epoxy vinyl ester resin, adopts the curing agent for initiating peroxide curing at low temperature to cure the prepreg resin, and 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 condition is milder than the prior art, the dependence on large-scale special equipment is reduced, and the mass production of enterprises is facilitated;
(2) The preparation method and the curing method are simple, the production cost is lower, the operation and the condition control are easy, crystalline crosslinking monomer thickened epoxy vinyl ester resin is adopted to replace the traditional alkali metal oxide, inorganic thixotropic agent or isocyanate, compared with the traditional thickening system, the high temperature and high pressure are required to reduce the viscosity of the resin to effectively fill the mold, the prepreg of the method has the viscosity requirement of good spreadability at normal temperature, the viscosity of the resin is rapidly reduced to effectively fill the mold 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 complex high-performance composite material component is greatly reduced;
(3) Meanwhile, the application adopts the crystallization crosslinking monomer and part of the low-volatility crosslinking monomer to endow the prepreg with the characteristics of no obvious smell and environmental friendliness in the molding process, so that the application has higher performance, lower cost and environmental friendliness compared with the prior art.
Detailed Description
The following description of the embodiments of the present application will clearly and fully describe the technical aspects of the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present application without making any inventive effort, are intended to fall within the scope of the present application.
The following is a further description of the solution of the present application with reference to examples:
in the following embodiments:
epoxy vinyl ester is available from ronwei 901 epoxy vinyl ester resin;
n-methylmaleimide is purchased from Hubei cloud magnesium technology;
n-cyclohexylmaleimide was purchased from Wuhan Kang Qiong Biomedicine;
tetrahydrophthalic anhydride is purchased from the chemical industry of deuzuron in the north of the lake;
maleic anhydride was purchased from shandong sink chemical;
diallyl phthalate was purchased from Shandong Luyuan chemical;
the 2, 5-dimethyl-2, 5-di (2-ethylhexanoyl peroxidation) hexane is purchased from Hubei Hongxin Ruiyu fine chemical industry;
the tert-butyl peroxy-2-ethylhexanoate is purchased from a catalpol-Hua auxiliary agent;
the tert-amyl peroxy-2-ethylhexanoate is purchased from a Zibo-n-Hua aid;
example 1
11kg of epoxy vinyl ester is weighed, heated to 60 ℃, then 1kg of diallyl phthalate is added, the mixture is stirred for 20 minutes under heat preservation, then 7.6kg of N-methyl maleimide is weighed, the mixture is added into a reaction system, the mixture is stirred for 40 minutes under heat preservation, the N-methyl maleimide is completely dissolved, the system is cooled to 45 ℃, 400g of 2, 5-dimethyl-2, 5-di (2-ethylhexanoyl peroxide) hexane is added, and the mixture is stirred for 5 minutes under the condition of keeping the temperature of 45 ℃ to obtain the resin.
And (3) making the high-strength glass fiber yarn enter epoxy vinyl resin in a molten state through a yarn spreader under a certain tension to obtain a limit prepreg in directional arrangement, extruding redundant epoxy vinyl ester resin through a glue extruding device, controlling the content of a resin matrix to be 25%, respectively covering the upper surface and the lower surface with a polyethylene film and fluorine-containing release paper, coiling, packaging in an aluminized plastic bag, boxing, and delivering into a freezer at the temperature of minus 20 ℃ to minus 10 ℃ for storage.
Example 2
14kg of epoxy vinyl ester is weighed, heated to 60 ℃, 1.8kg of diallyl isophthalate is added, the mixture is stirred for 30 minutes under heat preservation, 4kg of N-cyclohexylmaleimide is weighed, the mixture is added into a reaction system, the mixture is stirred for 60 minutes under heat preservation, the N-cyclohexylmaleimide is completely dissolved, the system is cooled to 50 ℃, 200g of tert-butyl peroxy-2-ethylhexanoate is added, and the mixture is stirred for 10 minutes under the condition of 50 ℃ to obtain the resin.
The high-strength glass fiber cloth is put into epoxy vinyl ester resin in a molten state under the assistance of a guide roller, the epoxy vinyl ester resin is reinforced and immersed by a heating roller, the content of a resin matrix is controlled to be 50%, the upper surface and the lower surface are respectively covered with a polyethylene film and fluorine-containing release paper, the polyethylene film and the fluorine-containing release paper are packaged in an aluminized plastic bag for boxing after being coiled, and the aluminized plastic bag is sent into a refrigeration house at the temperature of minus 20 ℃ to minus 10 ℃ for preservation.
Example 3
13kg of epoxy vinyl ester is weighed, heated to 70 ℃, then 2kg of diallyl terephthalate is added, the temperature is kept for stirring for 40min, then 5.9kg of tetrahydrophthalic anhydride is weighed, the mixture is added into a reaction system, the temperature is kept for stirring for 80min, the tetrahydrophthalic anhydride is completely dissolved, the system is cooled to 55 ℃, 100g of tert-amyl peroxy-2-ethylhexanoate is added, and the mixture is stirred for 15min under the condition of keeping the temperature at 55 ℃ to obtain the resin.
And (3) enabling the T700 carbon fiber yarns to enter epoxy vinyl ester resin in a molten state through a yarn spreader under a certain tension to obtain fiber prepregs which are arranged in an oriented mode, extruding redundant epoxy vinyl ester resin through a glue extruding device, controlling the content of a resin matrix to be 25%, respectively covering the upper surface and the lower surface with a polyethylene film and fluorine-containing release paper, coiling, packaging in an aluminum-plated plastic bag, boxing, and storing in a freezer at the temperature of minus 20 ℃ to minus 10 ℃.
Example 4
Heating 12kg of epoxy vinyl ester to 80 ℃, then adding 1.2kg of diallyl terephthalate, keeping the temperature and stirring for 40min, weighing 6.4kg of maleic anhydride, adding the mixture into a reaction system, continuing to keep the temperature and stirring for 60min, completely dissolving the maleic anhydride, then cooling the system to 50 ℃, adding 400g of tert-amyl peroxy-2-ethylhexanoate, and stirring for 10min at 50 ℃ to obtain the resin.
And (3) putting the T700 carbon fiber cloth into epoxy vinyl ester resin in a molten state under the assistance of a guide roller, carrying out reinforcement impregnation by a heating roller, extruding the redundant epoxy vinyl ester resin, controlling the content of a resin matrix to be 50%, respectively covering the upper surface and the lower surface with a polyethylene film and fluorine-containing release paper, coiling, packaging in an aluminized plastic bag, boxing, and delivering into a freezer at the temperature of minus 20 ℃ to minus 10 ℃ for preservation.
In examples 1 to 4 described above, the laying direction was kept uniform when the high-strength glass fiber yarns, the high-strength glass fiber cloth and the T700 carbon fiber cloth were stacked in layers.
Example 5
Tearing release paper on the surface of the prepreg prepared in the embodiment 1, paving the release paper in a mould to ensure that the prepreg is attached to the surface of the mould, tearing a polyethylene film, removing a second prepreg, tearing the release paper, paving the release paper on a first layer of prepreg, attaching the release paper to the first layer of prepreg, repeating the steps until the design thickness is reached, paving release cloth, a separation film and a glue absorption felt on the surface of the prepreg, sealing a prepreg forming area by using a vacuum bag, vacuumizing to the pressure of-0.09 MPa, introducing circulating water at the temperature of 98-100 ℃, and curing for 20min because the thickness of the prepreg in the mould is 2mm, and demolding after curing is completed to obtain a prepreg product.
Example 6
Tearing release paper on the surface of the prepreg prepared in the embodiment 2, paving the release paper in a mould to ensure that the prepreg is attached to the surface of the mould, tearing a polyethylene film, removing a second prepreg, tearing the release paper, paving the release paper on a first layer of prepreg, attaching the release paper to the first layer of prepreg, repeating the steps until the design thickness is reached, paving release cloth, a separation film and a glue absorption felt on the surface of the prepreg, sealing a prepreg forming area by using a vacuum bag, vacuumizing to the pressure of-0.09 MPa, introducing circulating water at the temperature of 98-100 ℃, and curing for 20min because the thickness of the prepreg in the mould is 2mm, and demolding after curing is completed to obtain a prepreg product.
Example 7
Tearing 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 a polyethylene film, removing a second prepreg, tearing the release paper, paving the release paper on a first layer of prepreg, attaching the release paper to the first layer of prepreg, repeating the steps until the design thickness is reached, paving release cloth, a separation film and a suction felt on the surface of the prepreg, sealing a prepreg molding area by using a vacuum bag, vacuumizing to the pressure of-0.09 MPa, putting the prepreg together with the mold in an oven, curing for 20 minutes at the temperature of 95-100 ℃ because the thickness of the prepreg in the mold is 2mm, and demolding after curing to obtain a prepreg product.
Example 8
Tearing release paper on the surface of the prepreg prepared in the embodiment 4, paving the release paper in a mold to ensure that the prepreg is attached to the surface of the mold, tearing a polyethylene film, removing a second prepreg, tearing the release paper, paving the release paper on a first layer of prepreg, attaching the release paper to the first layer of prepreg, repeating the steps until the design thickness is reached, paving release cloth, a separation film and a suction felt on the surface of the prepreg, sealing a prepreg molding area by using a vacuum bag, vacuumizing to the pressure of-0.09 MPa, putting the prepreg together with the mold in an oven, curing for 20 minutes at the temperature of 95-100 ℃ because the thickness of the prepreg in the mold is 2mm, and demolding after curing to obtain a prepreg product.
The prepreg products prepared in examples 5 to 8 above were smooth and flat in surface, stable in morphology and required to be obtained after performance compounding and curing.
Comparative example
The method comprises the steps of purchasing commercially available prepreg, tearing release paper on the surface of the prepreg, paving the prepreg in a mold to ensure that the prepreg is attached to the surface of the mold, tearing a polyethylene film, removing a second prepreg, tearing the release paper, paving the release paper on a first layer of prepreg, attaching the release paper to the first layer of prepreg, repeating the steps until the design thickness is achieved, paving release cloth on the surface of the prepreg, sealing a prepreg molding area by using a vacuum bag, vacuumizing to the pressure of-0.09 MPa, putting the prepreg together with the mold in an oven, curing for 20 minutes at the temperature of 95-100 ℃, demolding after curing to obtain a prepreg product, and not achieving the curing effect.
The prepreg products prepared in examples 5 to 8 and comparative example were respectively subjected to mechanical property test, the test equipment was a universal mechanical tester of 100 kilonewtons, the test items include measurement of tensile strength, tensile modulus, compressive strength, compressive modulus, flexural strength, flexural modulus and interlaminar shear strength of the prepreg products, the measurement directions of the tensile strength, tensile modulus, compressive strength, compressive modulus, flexural modulus and flexural strength were all radial directions of the corresponding fiber layers, the dimensions of the test sheets were unified to be 250mm in length, 25mm in width and 2mm in thickness, and the test results were as follows:
the results of the above examples and comparative examples show that, with the prepreg of the present application, curing can be completed in a relatively short period of time at a temperature of less than 100 ℃, and the cured product has good performance, while with the same conditions, the comparative examples cannot complete curing, and the final product cannot perform a test of partial mechanical properties, while the prepreg cured product of the present application has good mechanical properties, and compared with the prior art, the curing temperature and curing time are greatly reduced, and for enterprises, the production conditions of the prepreg product become simpler, and the popularization and application are easy.
The foregoing description of the preferred embodiments of the application is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the application.
Claims (6)
1. The energy-saving 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 as 100 percent:
epoxy vinyl ester 55-70%
Normal temperature crystallization monomer 20-38%
Vinyl monomer 5-10%
0.5-2% of curing agent;
the normal temperature crystallization monomer is one or more of N-methyl maleimide, N-cyclohexyl maleimide, tetrahydrophthalic anhydride and maleic anhydride; the vinyl monomer is diallyl phthalate;
the curing agent is one of 2, 5-dimethyl-2, 5-di (2-ethylhexanoyl peroxide) hexane, tert-butyl peroxy-2-ethylhexanoate and tert-amyl peroxy-2-ethylhexanoate.
2. The energy-saving and environment-friendly epoxy vinyl ester resin prepreg according to claim 1, wherein the diallyl phthalate is one or more of diallyl phthalate, diallyl isophthalate and diallyl terephthalate.
3. The energy efficient environmental protection epoxy vinyl ester resin prepreg of claim 1, wherein the reinforcing fiber is one of glass fiber yarn, glass fiber cloth, carbon fiber yarn and carbon fiber cloth.
4. A method for preparing the energy-saving and environment-friendly epoxy vinyl ester resin prepreg according to any one of claims 1 to 3, which is characterized by comprising the following steps:
step S1, heating epoxy vinyl ester to 60-80 ℃, adding diallyl phthalate, carrying out heat preservation and stirring for 20-40min, adding normal-temperature crystallization monomers, continuing to carry out heat preservation and stirring for 40-80min, cooling to 45-55 ℃, adding a curing agent, and carrying out heat preservation and stirring for 5-15min to obtain resin;
s2, heating the resin to enable the resin to enter a molten state, immersing the reinforced fiber into the resin in the molten state, extruding out excessive resin to obtain the prepreg, covering films on the upper surface and the lower surface of the prepreg, coiling and packaging, and then storing at-20 to-10 ℃.
5. The method for curing the energy-saving and environment-friendly epoxy vinyl ester resin prepreg according to claim 4, which is characterized by comprising the following steps:
tearing a film on one side of the prepreg, paving the film on the surface of a die, closely attaching the film, tearing a film on the other side of the prepreg, and selectively repeating the steps on the surface of the first layer of prepreg according to the design thickness of a product until the thickness requirement of the product is met;
sequentially spreading release cloth, a separation film and a glue absorbing felt on one surface of the prepreg far away from the die from inside to outside, sealing a prepreg molding 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 c, which was maintained, and the curing time was determined according to the thickness of the prepreg at 10 min/mm.
6. The method for curing an energy-saving and environment-friendly epoxy vinyl ester resin prepreg according to claim 5, wherein the method for raising the temperature of the prepreg to 95-100 ℃ comprises: introducing a heating medium at 95-100deg.C into the mold, or placing the prepreg together with the mold into a heating container, and heating to 95-100deg.C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111356095.7A CN114163670B (en) | 2021-11-16 | 2021-11-16 | Energy-saving environment-friendly epoxy vinyl ester resin prepreg, and preparation method and curing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111356095.7A CN114163670B (en) | 2021-11-16 | 2021-11-16 | Energy-saving environment-friendly epoxy vinyl ester resin prepreg, and preparation method and curing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114163670A CN114163670A (en) | 2022-03-11 |
| CN114163670B true CN114163670B (en) | 2023-12-01 |
Family
ID=80479266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111356095.7A Active CN114163670B (en) | 2021-11-16 | 2021-11-16 | Energy-saving environment-friendly epoxy vinyl ester resin prepreg, and preparation method and curing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114163670B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115091823B (en) * | 2022-08-25 | 2022-12-06 | 浙江葆润应用材料有限公司 | Fireproof composite material, preparation method and application of fireproof composite material in battery assembly |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242792A (en) * | 1997-10-14 | 2000-01-26 | 东丽株式会社 | Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| JP2008024787A (en) * | 2006-07-19 | 2008-02-07 | Mitsubishi Rayon Co Ltd | Radically polymerizable resin composition, prepreg, and fiber-reinforced composite material |
| CN102797157A (en) * | 2012-02-03 | 2012-11-28 | 金柏青 | Carbon fiber impregnating liquid, preparation method thereof and process for producing prepreg |
| CN103025775A (en) * | 2010-07-26 | 2013-04-03 | 三菱丽阳株式会社 | Resin composition, prepreg using same, and fiber-reinforced composite material |
| CN107090065A (en) * | 2017-06-22 | 2017-08-25 | 陕西生益科技有限公司 | High frequency resin composition and its application in prepreg and metal-clad laminate |
| CN107778782A (en) * | 2017-12-05 | 2018-03-09 | 镇江海威新材料科技有限公司 | A kind of epoxy vinyl ester resin prepreg and preparation method thereof of rapid curing, high-performance and low-cost |
| CN111187438A (en) * | 2020-02-10 | 2020-05-22 | 北京航空航天大学 | Preparation method of carbon fiber/toughened epoxy resin prepreg for vacuum bag forming process |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9034982B2 (en) * | 2009-08-12 | 2015-05-19 | Ashland Licensing And Intellectual Property, Llc | Formulations comprising isosorbide-modified unsaturated polyester resins and low profile additives which produce low shrinkage matrices |
-
2021
- 2021-11-16 CN CN202111356095.7A patent/CN114163670B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1242792A (en) * | 1997-10-14 | 2000-01-26 | 东丽株式会社 | Epoxy resin composition for fiber-reinforced composite material, prepreg, and fiber-reinforced composite material |
| JP2008024787A (en) * | 2006-07-19 | 2008-02-07 | Mitsubishi Rayon Co Ltd | Radically polymerizable resin composition, prepreg, and fiber-reinforced composite material |
| CN103025775A (en) * | 2010-07-26 | 2013-04-03 | 三菱丽阳株式会社 | Resin composition, prepreg using same, and fiber-reinforced composite material |
| CN102797157A (en) * | 2012-02-03 | 2012-11-28 | 金柏青 | Carbon fiber impregnating liquid, preparation method thereof and process for producing prepreg |
| CN107090065A (en) * | 2017-06-22 | 2017-08-25 | 陕西生益科技有限公司 | High frequency resin composition and its application in prepreg and metal-clad laminate |
| CN107778782A (en) * | 2017-12-05 | 2018-03-09 | 镇江海威新材料科技有限公司 | A kind of epoxy vinyl ester resin prepreg and preparation method thereof of rapid curing, high-performance and low-cost |
| CN111187438A (en) * | 2020-02-10 | 2020-05-22 | 北京航空航天大学 | Preparation method of carbon fiber/toughened epoxy resin prepreg for vacuum bag forming process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114163670A (en) | 2022-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6778309B2 (en) | Thermoplastic (meth) acrylic resin composite material obtained by in-site polymerization and its use | |
| US7887916B2 (en) | Process for producing sandwich structure and adhesive film used therefor | |
| CN106808715B (en) | A kind of preparation method of carbon fibre composite auto parts and components | |
| CN114163670B (en) | Energy-saving environment-friendly epoxy vinyl ester resin prepreg, and preparation method and curing method thereof | |
| CN105671937A (en) | Modification method of ramie fibers using as environment-friendly composite material reinforcement | |
| CN1916477A (en) | Hypothermal moment tube made from composite material, and prepartion method | |
| CN1990540A (en) | Fiber reinforced thermolplastic composite material preparation method | |
| CN109563291B (en) | Composition comprising a fibrous material, a multistage polymer and a (meth) acrylic polymer, method for the preparation thereof and use thereof | |
| CN102146196A (en) | Preparation method of high damping epoxy resin composite | |
| CN103525115A (en) | Low-density bulk molding compound (BMC) and preparation method thereof | |
| WO2015106482A1 (en) | Preparation method for high-performance fibre composite article | |
| CN104031358A (en) | Unsaturated resin fiberglass prepreg for low-temperature low-pressure molding as well as preparation method and application of unsaturated resin fiberglass prepreg | |
| CN107778782A (en) | A kind of epoxy vinyl ester resin prepreg and preparation method thereof of rapid curing, high-performance and low-cost | |
| Kafi et al. | Effect of manufacturing process on the flexural, fracture toughness, and thermo-mechanical properties of bio-composites | |
| CN102675796A (en) | Preparation method and applications of low-water-absorption polymethacrylimide foamed plastics | |
| CN112265337A (en) | Amorphous fiber-based composite material for structural health monitoring and method and application thereof | |
| CN107652645A (en) | A kind of low-temp low-pressure shaping unsaturated polyester resin glass fiber prepreg and preparation method thereof | |
| CN109897375B (en) | High-strength flexible epoxy resin modified cyanate ester resin/carbon fiber composite shape memory material and preparation method thereof | |
| CN114670466A (en) | Laminate with high post-impact compressive strength and method of making same | |
| CN109181246A (en) | A kind of high wearable Combined baling belt masterbatch | |
| CN111040163B (en) | Bismaleimide resin, air bag for autoclave molding and preparation method thereof | |
| US11879030B2 (en) | Liquid composition comprising three initiators, its process of polymerization, use and material or composition obtained following polymerization of composition | |
| Xiang et al. | Preparation of fixed length carbon fiber reinforced plastic composite sheets with isotropic mechanical properties | |
| EP3938408A1 (en) | Liquid composition comprising a wax compound, its process of polymerization, use and material or composition obtained following polymerization of composition | |
| CN117264372B (en) | Light high-strength sandwich-structure epoxy resin foam material, reinforcing layer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |