CN115975346B - Epoxy resin premix for OOA cured prepreg and preparation method thereof - Google Patents
Epoxy resin premix for OOA cured prepreg and preparation method thereof Download PDFInfo
- Publication number
- CN115975346B CN115975346B CN202310264813.0A CN202310264813A CN115975346B CN 115975346 B CN115975346 B CN 115975346B CN 202310264813 A CN202310264813 A CN 202310264813A CN 115975346 B CN115975346 B CN 115975346B
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- parts
- ooa
- curing agent
- premix
- 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
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 153
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 153
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 61
- 239000012745 toughening agent Substances 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 7
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 31
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000013034 phenoxy resin Substances 0.000 claims description 7
- 229920006287 phenoxy resin Polymers 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 229920006260 polyaryletherketone Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 12
- 239000004917 carbon fiber Substances 0.000 abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002131 composite material Substances 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 230000035939 shock Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- 239000004843 novolac epoxy resin Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 12
- 239000004744 fabric Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000010998 test method Methods 0.000 description 7
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/40—Weight reduction
Landscapes
- Reinforced Plastic Materials (AREA)
- Epoxy Resins (AREA)
Abstract
The invention relates to the technical field of preparation of carbon fiber resin matrix composite materials, in particular to an epoxy resin premix for an OOA cured prepreg and a preparation method thereof. Wherein, the epoxy resin premix for the OOA curing prepreg comprises, by weight, 20-40 parts of epoxy resin, 10-20 parts of toughening agent, 10-20 parts of surface modifier, 7-15 parts of curing agent and 3-5 parts of accelerator; the surface modifier is at least one of calcium carbonate, silicon dioxide and aluminum silicate. The invention can ensure the stability of the surface smoothness of the cured product, and can improve the wear resistance, the thermal stability and the shock resistance of the premix at the same time, thereby being beneficial to the appearance of the epoxy resin premix with smooth and flat appearance after the curing of the OOA technology.
Description
Technical Field
The invention relates to the technical field of preparation of carbon fiber resin matrix composite materials, in particular to an epoxy resin premix for an OOA cured prepreg and a preparation method thereof.
Background
The high-performance epoxy resin-based carbon fiber composite material not only has excellent light weight performance, but also has mechanical properties not lower than those of metal, and plays an important role in the fields of aerospace and national defense. The epoxy resin premix for the carbon fiber prepreg is an important front-end raw material of a composite material dispersing system part, and usually the carbon fiber prepreg needs to be cured by an autoclave, but the autoclave curing has the defects of high process cost, limited size of the part, high energy consumption, low efficiency, unfavorable mass production and the like.
The non-autoclave (OOA) molding technology is a low-cost composite material molding technology which does not need an autoclave, and only eliminates and compacts bubbles in a material by virtue of vacuum pressure, thereby achieving the performance equivalent to that of the autoclave molding composite material. The OOA forming technology has the advantages of uniform pressurization, uniform product performance, reduction of bubbles in the product, complex forming, large-scale parts and the like, but the product has the problems of poor surface smoothness and evenness and relatively poor partial mechanical properties.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of poor surface smoothness and relatively poor partial mechanical properties of the existing OOA technical product, thereby providing the epoxy resin for the OOA curing prepreg and the preparation method thereof.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the epoxy resin premix for the OOA cured prepreg comprises, by weight, 20-40 parts of epoxy resin, 10-20 parts of a toughening agent, 10-20 parts of a surface modifier, 7-15 parts of a curing agent and 3-5 parts of an accelerator;
the surface modifier is at least one of calcium carbonate, silicon dioxide and aluminum silicate.
Preferably, the epoxy resin is a mixture of liquid bisphenol a epoxy resin, solid bisphenol a epoxy resin, liquid phenolic epoxy resin and solid phenolic epoxy resin, wherein the weight parts of the liquid bisphenol a epoxy resin, the solid bisphenol a epoxy resin, the liquid phenolic epoxy resin and the solid phenolic epoxy resin are not less than 5 parts; the liquid bisphenol A epoxy resin includes, but is not limited to, NPEL-127, NPEL-128, the solid bisphenol A epoxy resin includes, but is not limited to, NPES-901, NPES-902, the solid novolac epoxy resin includes, but is not limited to, NPCN-701, NPCN-702, NPCN-703, NPCN-704, and the liquid novolac epoxy resin includes, but is not limited to, NPPN-631, NPPN-638S.
Preferably, the toughening agent is at least one of phenoxy resin (PKHH), polyvinyl alcohol Ding Quanzhi (PVB), polyethylene (PE), polyaryletherketone and polyethersulfone.
Preferably, the curing agent is dicyandiamide.
Preferably, the accelerator is at least one of organic urea, thiourea and imidazole compounds.
The invention also provides the epoxy resin premix for the OOA cured prepreg and a preparation method thereof, and the epoxy resin premix comprises the following steps:
acquisition of epoxy resin 1 and epoxy resin 2: dividing epoxy resin into two parts, namely epoxy resin 1 and epoxy resin 2;
obtaining curing agent paste: adding a curing agent and an accelerator into the epoxy resin 1 and uniformly mixing to obtain curing agent paste;
acquisition of premix: heating the epoxy resin 2 to 100-120 ℃, adding the toughening agent and the surface modifier, stirring and mixing uniformly, cooling to 60-70 ℃, adding the curing agent paste, and stirring uniformly to obtain the epoxy resin premix for the OOA curing prepreg.
Preferably, the method further comprises the step of uniformly mixing the epoxy resin before dividing the epoxy resin into two parts;
the mode of mixing evenly is as follows: heating at 60-80deg.C, stirring for 30-60 min.
Preferably, in the step of obtaining the curing agent paste, the temperature of the epoxy resin 1 is lowered to room temperature before the curing agent and the accelerator are added to the epoxy resin 1.
Preferably, in the step of obtaining the curing agent paste, the mixing of the epoxy resin 1 with the curing agent and the accelerator is performed using a high-speed disperser and a three-roll mill.
Preferably, in the step of obtaining the premix, the stirring time of the epoxy resin 2, the toughening agent and the surface modifier is 30-60 min;
and/or stirring for 15-30 min after adding the curing agent paste.
The technical scheme of the invention has the following advantages:
1. the epoxy resin premix for the OOA cured prepreg comprises, by weight, 20-40 parts of epoxy resin, 10-20 parts of a toughening agent, 10-20 parts of a surface modifier, 7-15 parts of a curing agent and 3-5 parts of an accelerator; the surface modifier is at least one of calcium carbonate, silicon dioxide and aluminum silicate. In the curing process, the surface modifier can fill the surface defect formed by the epoxy resin in the curing process through intermolecular force and smaller surface tension diffusion of the surface modifier and the epoxy resin, and perform anchoring action in a group gap between the surface modifier and the epoxy resin and between the surface modifier and the curing agent, so that the stability of the surface smoothness of the cured product is ensured, and meanwhile, the wear resistance, the thermal stability and the impact resistance of the premix are improved, and the appearance of the epoxy resin premix with smoothness after the epoxy resin premix is cured by an OOA process is further facilitated.
2. According to the epoxy resin premix for the OOA cured prepreg, the bisphenol A epoxy resin is adopted to adjust the viscosity of the system, so that the system is suitable for a hot melting process; the phenolic epoxy resin is adopted, so that the crosslinking density of the system is improved, and the temperature resistance, the strength and the corrosion resistance are improved; the addition of the toughening agent can improve the impact resistance and film forming property of the resin system; the curing temperature of the system can be controlled between 120 ℃ and 150 ℃ by adding the curing agent and the accelerator, so that the OOA curing process can be stably carried out.
3. The curing mode of the prepreg manufactured by the epoxy resin premix for the OOA curing prepreg does not need to be filled with pressurized gas like autoclave curing, so that the cost is saved, and the curing efficiency is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is an apparent view of laminates obtained by OOA curing in examples 1-4 according to the invention;
FIG. 2 is an apparent view of a laminate obtained by OOA curing in comparative example 1 according to the present invention, respectively;
FIG. 3 is an apparent view of a laminate obtained by OOA curing in comparative example 2 according to the present invention, respectively;
FIG. 4 is an apparent view of laminates obtained by OOA curing in comparative example 3 according to the present invention, respectively.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
In the examples below, the weight of each serving is 1kg.
Example 1
An epoxy resin premix for OOA cured prepregs comprising, in parts by weight:
epoxy resin: 5 parts of solid bisphenol A epoxy resin (NPES-902), 5 parts of liquid bisphenol A epoxy resin (NPEL-127), 5 parts of solid novolac epoxy resin (NPCN-702), 5 parts of liquid novolac epoxy resin (NPPN-631);
toughening agent: 10 parts of phenoxy resin (PKHH);
surface modifying agent: 10 parts of silicon dioxide;
curing agent: 7 parts of dicyandiamide;
and (3) an accelerator: 3 parts of methyl thiourea.
The preparation method of the epoxy resin premix for the OOA cured prepreg comprises the following steps:
1) Heating epoxy resin to 60 ℃ to melt, stirring and mixing for 30 min, and then dividing the mixture into two parts, namely epoxy resin 1 and epoxy resin 2;
2) Cooling the epoxy resin 1 obtained in the step 1) to room temperature, adding a curing agent and an accelerator, and uniformly mixing by adopting a high-speed dispersing machine and a three-roller mill to obtain curing agent paste;
3) Heating the epoxy resin 2 obtained in the step 1) to 100 ℃, adding a toughening agent and a surface modifier, mixing for 30 min, then cooling to 60 ℃, adding the curing agent paste obtained in the step 2), and uniformly stirring for 15 min to obtain the epoxy resin premix for the OOA curing prepreg.
The epoxy resin premix for OOA cured prepregs obtained in the above examples was subjected to main performance tests, and the test items, test methods, and test results are shown in table 1 below;
TABLE 1
。
Preparing a prepreg with the epoxy resin premix content of 40% for the OOA cured prepreg by using a domestic T300-grade 200gsm carbon fiber twill fabric from the epoxy resin premix for the OOA cured prepreg obtained in the above example, and curing the prepreg by using OOA and an autoclave respectively to obtain a laminated board, wherein the appearance of the laminated board obtained by OOA curing is shown in (a) of FIG. 1, and the main mechanical properties of the laminated board obtained by OOA and autoclave curing are shown in the following Table 2;
TABLE 2
。
Example 2
An epoxy resin premix for OOA cured prepregs comprising, in parts by weight:
epoxy resin: 10 parts of solid bisphenol A epoxy resin (NPES-902), 10 parts of liquid bisphenol A epoxy resin (NPEL-127), 10 parts of solid novolac epoxy resin (NPCN-702), 10 parts of liquid novolac epoxy resin (NPPN-631);
toughening agent: 20 parts of phenoxy resin (PKHH);
surface modifying agent: 20 parts of silicon dioxide;
curing agent: 15 parts of dicyandiamide;
and (3) an accelerator: 5 parts of methyl thiourea.
The preparation method of the epoxy resin premix for the OOA cured prepreg comprises the following steps:
1) Heating the epoxy resin to 80 ℃ to melt, stirring and mixing for 60 min, and then dividing the mixture into two parts, namely epoxy resin 1 and epoxy resin 2;
2) Cooling the epoxy resin 1 obtained in the step 1) to room temperature, adding a curing agent and an accelerator, and uniformly mixing by adopting a high-speed dispersing machine and a three-roller mill to obtain curing agent paste;
3) Heating the epoxy resin 2 obtained in the step 1) to 120 ℃, adding a toughening agent and a surface modifier, mixing for 60 min, then cooling to 70 ℃, adding the curing agent paste obtained in the step 2), and uniformly stirring for 30 min to obtain the epoxy resin premix for the OOA curing prepreg.
The epoxy resin premix for OOA cured prepregs obtained in the above examples was subjected to main performance tests, and the test items, test methods, and test results are shown in table 3 below;
TABLE 3 Table 3
。
Preparing a prepreg with the epoxy resin premix content of 40% for the OOA cured prepreg by using a domestic T300-grade 200gsm carbon fiber twill fabric from the epoxy resin premix for the OOA cured prepreg obtained in the above example, and curing the prepreg by using OOA and an autoclave respectively to obtain a laminated board, wherein the appearance of the laminated board obtained by OOA curing is shown in (b) of FIG. 1, and the main mechanical properties of the laminated board obtained by OOA and autoclave curing are shown in the following Table 4;
TABLE 4 Table 4
。
Example 3
An epoxy resin premix for OOA cured prepregs comprising, in parts by weight:
epoxy resin: 5 parts of solid bisphenol A epoxy resin (NPES-901), 5 parts of liquid bisphenol A epoxy resin (NPEL-128), 5 parts of solid novolac epoxy resin (NPCN-701) and 5 parts of liquid novolac epoxy resin (NPPN-638S);
toughening agent: 5 parts of polyethersulfone and 5 parts of polyaryletherketone;
surface modifying agent: 5 parts of calcium carbonate and 5 parts of aluminum silicate;
curing agent: 7 parts of dicyandiamide;
and (3) an accelerator: 2 parts of organic urea UR300 and 1 part of N-methylimidazole.
The preparation method of the epoxy resin premix for the OOA cured prepreg comprises the following steps:
1) Heating the epoxy resin to 70 ℃ for melting, stirring and mixing for 45 min, and then dividing the mixture into two parts, namely epoxy resin 1 and epoxy resin 2;
2) Cooling the epoxy resin 1 obtained in the step 1) to room temperature, adding a curing agent and an accelerator, and uniformly mixing by adopting a high-speed dispersing machine and a three-roller mill to obtain curing agent paste;
3) Heating the epoxy resin 2 obtained in the step 1) to 110 ℃, adding a toughening agent and a surface modifier, mixing for 60 min, then cooling to 65 ℃, adding the curing agent paste obtained in the step 2), and uniformly stirring for 23 min to obtain the epoxy resin premix for the OOA curing prepreg.
The epoxy resin premix for OOA cured prepregs obtained in the above examples was subjected to main performance tests, and the test items, test methods, and test results are shown in table 5 below;
TABLE 5
。
Preparing a prepreg with the epoxy resin premix content of 40% for the OOA cured prepreg by using a domestic T300-grade 200gsm carbon fiber twill fabric from the epoxy resin premix for the OOA cured prepreg obtained in the above example, and curing the prepreg by using OOA and an autoclave respectively to obtain a laminated board, wherein the appearance of the laminated board obtained by OOA curing is shown in (c) of FIG. 1, and the main mechanical properties of the laminated board obtained by OOA and autoclave curing are shown in the following Table 6;
TABLE 6
。
Example 4
An epoxy resin premix for OOA cured prepregs comprising, in parts by weight:
epoxy resin: 5 parts of solid bisphenol A epoxy resin (NPES-902), 5 parts of liquid bisphenol A epoxy resin (NPEL-128), 5 parts of solid novolac epoxy resin (NPCN-703), 5 parts of liquid novolac epoxy resin (NPPN-638S);
toughening agent: 5 parts of Polyethylene (PE), 5 parts of polyvinyl acetal Ding Quanzhi;
surface modifying agent: 10 parts of aluminum silicate;
curing agent: 7 parts of dicyandiamide;
and (3) an accelerator: 3 parts of N-methylimidazole.
The preparation method of the epoxy resin premix for the OOA cured prepreg comprises the following steps:
1) Heating epoxy resin to 60 ℃ to melt, stirring and mixing for 30 min, and then dividing the mixture into two parts, namely epoxy resin 1 and epoxy resin 2;
2) Cooling the epoxy resin 1 obtained in the step 1) to room temperature, adding a curing agent and an accelerator, and uniformly mixing by adopting a high-speed dispersing machine and a three-roller mill to obtain curing agent paste;
3) Heating the epoxy resin 2 obtained in the step 1) to 100 ℃, adding a toughening agent and a surface modifier, mixing for 30 min, then cooling to 60 ℃, adding the curing agent paste obtained in the step 2), and uniformly stirring for 15 min to obtain the epoxy resin premix for the OOA curing prepreg.
The epoxy resin premix for OOA cured prepregs obtained in the above examples was subjected to main performance tests, and the test items, test methods, and test results are shown in table 7 below;
TABLE 7
。
Preparing a prepreg with the epoxy resin premix content of 40% for the OOA cured prepreg by using a domestic T300-grade 200gsm carbon fiber twill fabric from the epoxy resin premix for the OOA cured prepreg obtained in the above example, and curing the prepreg by using OOA and an autoclave respectively to obtain a laminated board, wherein the appearance of the laminated board obtained by OOA curing is shown in (d) of FIG. 1, and the main mechanical properties of the laminated board obtained by OOA and autoclave curing are shown in the following Table 8;
TABLE 8
。
Comparative example 1
An epoxy resin premix for OOA cured prepregs comprising, in parts by weight:
epoxy resin: 5 parts of solid bisphenol A epoxy resin (NPES-902), 5 parts of liquid bisphenol A epoxy resin (NPEL-127), 5 parts of solid novolac epoxy resin (NPCN-702), 5 parts of liquid novolac epoxy resin (NPPN-631);
toughening agent: 10 parts of phenoxy resin (PKHH);
surface modifying agent: 5 parts of silicon dioxide;
curing agent: 7 parts of dicyandiamide;
and (3) an accelerator: 3 parts of methyl thiourea.
The preparation method of the epoxy resin premix for the OOA cured prepreg comprises the following steps:
1) Heating epoxy resin to 60 ℃ to melt, stirring and mixing for 30 min, and then dividing the mixture into two parts, namely epoxy resin 1 and epoxy resin 2;
2) Cooling the epoxy resin 1 obtained in the step 1) to room temperature, adding a curing agent and an accelerator, and uniformly mixing by adopting a high-speed dispersing machine and a three-roller mill to obtain curing agent paste;
3) Heating the epoxy resin 2 obtained in the step 1) to 100 ℃, adding a toughening agent and a surface modifier, mixing for 30 min, then cooling to 60 ℃, adding the curing agent paste obtained in the step 2), and uniformly stirring for 15 min to obtain the epoxy resin premix for the OOA curing prepreg.
The epoxy resin premix for the OOA cured prepreg obtained in the above comparative example was subjected to main performance test, and the test items, test methods, test results are shown in table 9 below;
TABLE 9
。
Preparing epoxy resin premix for OOA cured prepreg obtained in the above comparative example into prepreg with 40% of epoxy resin premix content for OOA cured prepreg by using domestic T300 grade 200gsm carbon fiber twill fabric, and curing by using OOA and autoclave respectively to obtain laminated board, wherein the appearance of the laminated board obtained by OOA curing is shown in figure 2, and the main mechanical properties of the laminated board obtained by OOA and autoclave curing are shown in the following table 10;
table 10
。
The in-plane shear strength and in-plane shear modulus of the laminated board obtained by OOA curing have a remarkable decrease trend, and more pinhole defects appear on appearance, and the apparent effect is inferior to that of autoclave curing.
Comparative example 2
An epoxy resin premix for OOA cured prepregs comprising, in parts by weight:
epoxy resin: 5 parts of solid bisphenol A epoxy resin (NPES-902), 5 parts of liquid bisphenol A epoxy resin (NPEL-127), 5 parts of solid novolac epoxy resin (NPCN-702), 5 parts of liquid novolac epoxy resin (NPPN-631);
toughening agent: 10 parts of phenoxy resin (PKHH);
surface modifying agent: no addition is made;
curing agent: 7 parts of dicyandiamide;
and (3) an accelerator: 3 parts of methyl thiourea.
The preparation method of the epoxy resin premix for the OOA cured prepreg comprises the following steps:
1) Heating epoxy resin to 60 ℃ to melt, stirring and mixing for 30 min, and then dividing the mixture into two parts, namely epoxy resin 1 and epoxy resin 2;
2) Cooling the epoxy resin 1 obtained in the step 1) to room temperature, adding a curing agent and an accelerator, and uniformly mixing by adopting a high-speed dispersing machine and a three-roller mill to obtain curing agent paste;
3) Heating the epoxy resin 2 obtained in the step 1) to 100 ℃, adding a toughening agent and a surface modifier, mixing for 30 min, then cooling to 60 ℃, adding the curing agent paste obtained in the step 2), and uniformly stirring for 15 min to obtain the epoxy resin premix for the OOA curing prepreg.
The epoxy resin premix for OOA cured prepregs obtained in the above comparative example was subjected to main performance tests, and the test items, test methods, and test results are shown in table 11 below;
TABLE 11
。
Preparing epoxy resin premix for OOA cured prepreg obtained in the above comparative example into prepreg with 40% of epoxy resin premix content for OOA cured prepreg by using domestic HF 20-grade 200gsm carbon fiber twill fabric, and curing by using OOA and autoclave respectively to obtain laminated board, wherein the appearance of the laminated board obtained by OOA curing is shown in figure 3, and the main mechanical properties of the laminated board obtained by OOA and autoclave curing are shown in the following table 12;
table 12
。
In the test sample, the mechanical properties of the plate are affected by the defects of the OOA cured part, such as lack of glue, and the like, and compared with an autoclave process, most of the mechanical properties are obviously reduced, so that the overall mechanical property result is lower.
Comparative example 3
An epoxy resin premix for OOA cured prepregs comprising, in parts by weight:
epoxy resin: 5 parts of solid bisphenol A epoxy resin (NPES-902), 5 parts of liquid bisphenol A epoxy resin (NPEL-127), 5 parts of solid novolac epoxy resin (NPCN-702), 5 parts of liquid novolac epoxy resin (NPPN-631);
toughening agent: 10 parts of phenoxy resin (PKHH);
surface modifying agent: 10 parts of sodium stearate;
curing agent: 7 parts of dicyandiamide;
and (3) an accelerator: 3 parts of methyl thiourea.
The preparation method of the epoxy resin premix for the OOA cured prepreg comprises the following steps:
1) Heating epoxy resin to 60 ℃ to melt, stirring and mixing for 30 min, and then dividing the mixture into two parts, namely epoxy resin 1 and epoxy resin 2;
2) Cooling the epoxy resin 1 obtained in the step 1) to room temperature, adding a curing agent and an accelerator, and uniformly mixing by adopting a high-speed dispersing machine and a three-roller mill to obtain curing agent paste;
3) Heating the epoxy resin 2 obtained in the step 1) to 100 ℃, adding a toughening agent and a surface modifier, mixing for 30 min, then cooling to 60 ℃, adding the curing agent paste obtained in the step 2), and uniformly stirring for 15 min to obtain the epoxy resin premix for the OOA curing prepreg.
The epoxy resin premix for OOA cured prepregs obtained in the above examples was subjected to main performance tests, and the test items, test methods, and test results are shown in table 13 below;
TABLE 13
。
Preparing epoxy resin premix for OOA cured prepreg obtained in the above comparative example into prepreg with 40% of epoxy resin premix content for OOA cured prepreg by using domestic T300 grade 200gsm carbon fiber twill fabric, and curing by using OOA and autoclave respectively to obtain laminated board, wherein the appearance of the laminated board obtained by OOA curing is shown in figure 4, and the main mechanical properties of the laminated board obtained by OOA and autoclave curing are shown in the following table 14;
TABLE 14
。
In the test sample piece, the OOA cured part of the test sample piece still has some uneven grain defects to influence the mechanical properties of the plate, so that the mechanical properties of the test sample piece are low.
From the test results of examples 1 to 4 and comparative examples 1 to 3 and fig. 1 to 4, it is understood that the surface modifier in the epoxy resin premix is reduced, not added or replaced, the appearance of the laminate obtained by curing through the OOA process is defective, and there is a significant decrease in part of the mechanical properties of the laminate, whereas the laminate obtained by curing the epoxy resin premix prepared by the composition and the formulation of the present invention is smooth and flat in appearance, and excellent in mechanical properties, without a significant decrease in mechanical properties compared with the laminate obtained by curing in an autoclave.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. The epoxy resin premix for the OOA cured prepreg is characterized by comprising, by weight, 20-40 parts of epoxy resin, 10-20 parts of a toughening agent, 10-20 parts of a surface modifier, 7-15 parts of a curing agent and 3-5 parts of an accelerator;
the surface modifier is at least one of calcium carbonate, silicon dioxide and aluminum silicate;
the epoxy resin is a mixture of liquid bisphenol A epoxy resin, solid bisphenol A epoxy resin, liquid phenolic epoxy resin and solid phenolic epoxy resin, wherein the weight parts of the liquid bisphenol A epoxy resin, the solid bisphenol A epoxy resin, the liquid phenolic epoxy resin and the solid phenolic epoxy resin are not less than 5 parts;
the toughening agent is at least one of phenoxy resin, polyvinyl alcohol Ding Quanzhi, polyethylene, polyaryletherketone and polyethersulfone.
2. The epoxy resin premix for OOA cured prepregs according to claim 1, wherein the curing agent is dicyandiamide.
3. The epoxy resin premix for OOA-cured prepregs according to claim 1 or 2, wherein the accelerator is at least one of organic urea, thiourea, imidazole compounds.
4. A method for preparing an epoxy resin premix for OOA cured prepreg according to any one of claims 1 to 3, comprising the steps of:
acquisition of epoxy resin 1 and epoxy resin 2: dividing epoxy resin into two parts, namely epoxy resin 1 and epoxy resin 2;
obtaining curing agent paste: adding a curing agent and an accelerator into the epoxy resin 1 and uniformly mixing to obtain curing agent paste;
acquisition of premix: heating the epoxy resin 2 to 100-120 ℃, adding the toughening agent and the surface modifier, stirring and mixing uniformly, cooling to 60-70 ℃, adding the curing agent paste, and stirring uniformly to obtain the epoxy resin premix for the OOA curing prepreg.
5. The method according to claim 4, further comprising the step of uniformly mixing the epoxy resin before dividing the epoxy resin into two parts;
the mode of mixing evenly is as follows: heating at 60-80deg.C, stirring for 30-60 min.
6. The method according to claim 4, wherein in the step of obtaining the curing agent paste, the temperature of the epoxy resin 1 is lowered to room temperature before the curing agent and the accelerator are added to the epoxy resin 1.
7. The method according to claim 4, wherein in the step of obtaining the curing agent paste, the mixing of the epoxy resin 1 with the curing agent and the accelerator is performed using a high-speed disperser and a three-roll mill.
8. The method according to claim 4, wherein in the step of obtaining the pre-mixture, the epoxy resin 2, the toughening agent and the surface modifier are stirred for 30 to 60 minutes;
and/or stirring for 15-30 min after adding the curing agent paste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310264813.0A CN115975346B (en) | 2023-03-13 | 2023-03-13 | Epoxy resin premix for OOA cured prepreg and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310264813.0A CN115975346B (en) | 2023-03-13 | 2023-03-13 | Epoxy resin premix for OOA cured prepreg and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115975346A CN115975346A (en) | 2023-04-18 |
| CN115975346B true CN115975346B (en) | 2023-07-28 |
Family
ID=85958186
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310264813.0A Active CN115975346B (en) | 2023-03-13 | 2023-03-13 | Epoxy resin premix for OOA cured prepreg and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115975346B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116606529B (en) * | 2023-07-19 | 2023-09-22 | 常州天启新新科技有限公司 | Low-temperature cured epoxy resin, preparation method, prepreg, composite material and application |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI494340B (en) * | 2010-08-02 | 2015-08-01 | Taiwan Union Technology Corp | Epoxy resin composition, and prepreg and printed wiring board using the same |
| US8895148B2 (en) * | 2011-11-09 | 2014-11-25 | Cytec Technology Corp. | Structural adhesive and bonding application thereof |
| CN112654656B (en) * | 2018-08-31 | 2024-02-27 | 陶氏环球技术有限责任公司 | Epoxy composite formula |
| CN113512273B (en) * | 2021-07-27 | 2023-06-09 | 上海复合材料科技有限公司 | OoA molding epoxy resin composition for prepreg by hot-melt method |
-
2023
- 2023-03-13 CN CN202310264813.0A patent/CN115975346B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN115975346A (en) | 2023-04-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111187438B (en) | Preparation method of carbon fiber/toughened epoxy resin prepreg for vacuum bag forming process | |
| CN115975346B (en) | Epoxy resin premix for OOA cured prepreg and preparation method thereof | |
| CN102615887B (en) | Light high-strength composite material with density less than that of water, and preparation method thereof | |
| CN104945885A (en) | Preparing method of epoxy resin carbon fiber prepreg | |
| CN105038142A (en) | Preparing method of hot-melt prepreg of novolac epoxy resin | |
| CN107722595B (en) | Preparation method of fiber-graphene-thermoplastic polyarylether multi-scale composite material | |
| CN110885535A (en) | Preparation method of epoxy resin composition suitable for autoclave initial pressurization | |
| CN110117409A (en) | A method of using multi-walled carbon nanotube toughening composition interlayer | |
| CN113136089A (en) | Rapid curing wave-transparent composite material and preparation method thereof | |
| CN105109068A (en) | Method for preparing presoak materials for forming non-hot-pressing tank | |
| CN117341227A (en) | High-strength carbon fiber shell forming process for unmanned aerial vehicle body | |
| CN110527129B (en) | Polyether-ether-ketone porous foam material and preparation method thereof | |
| CN108587067B (en) | High-modulus high-toughness epoxy resin carbon fiber prepreg and preparation method thereof | |
| CN107353775A (en) | Carbon fiber enhancement resin base composite material retardant surfaces film and preparation method thereof | |
| CN111574953A (en) | High-temperature-resistant honeycomb core strip glue, and preparation method and application thereof | |
| CN114015198A (en) | Preparation method of intermediate-temperature cured prepreg epoxy resin with optimized process | |
| CN111016377B (en) | Sandwich structure composite material and OOA preparation method thereof | |
| CN107868400A (en) | Intermediate temperature setting prepreg resin matrix and preparation method thereof | |
| CN113278254A (en) | Rapid curing flame-retardant insulating resin for fiber prepreg and preparation method thereof | |
| CN114907673B (en) | Epoxy molding composite material and preparation method thereof | |
| CN116063819B (en) | Medium-temperature curing epoxy resin premix for unmanned aerial vehicle structural member and preparation method | |
| CN115449219B (en) | Silica aerogel quartz fiber polyimide ternary composite material and preparation method and application thereof | |
| CN114044922B (en) | Nano alloy thermoplastic particles, nano alloy film, and preparation method and application thereof | |
| CN117050468A (en) | Preparation method of epoxy resin for prepreg and preparation method of prepreg | |
| CN117229602A (en) | Hot-in hot-out rapid prototyping prepreg and preparation method of composite material |
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 |