CN116082798B - Toughening modified epoxy resin composition, composite material and preparation method thereof - Google Patents
Toughening modified epoxy resin composition, composite material and preparation method thereof Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 175
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 175
- 239000000203 mixture Substances 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 108
- 239000004005 microsphere Substances 0.000 claims abstract description 53
- 239000011258 core-shell material Substances 0.000 claims abstract description 50
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 31
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000004917 carbon fiber Substances 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 19
- 238000005191 phase separation Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 9
- 239000006185 dispersion Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007791 liquid phase Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 23
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 13
- 239000002105 nanoparticle Substances 0.000 abstract description 11
- 230000002776 aggregation Effects 0.000 abstract description 7
- 239000012792 core layer Substances 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 230000009467 reduction Effects 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000005060 rubber Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920000881 Modified starch Polymers 0.000 description 2
- 239000004368 Modified starch Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000007656 fracture toughness test Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000019426 modified starch Nutrition 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000088 plastic resin Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- 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
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a toughened and modified epoxy resin composition, a composite material and a preparation method thereof, wherein the epoxy resin composition comprises the following components in parts by mass: 100 parts of epoxy resin and SiO with core-shell structure 2 2-20 parts of polysulfone microsphere and 20-25 parts of curing agent. The toughened and modified epoxy resin composition and the composite material are prepared by adding SiO with a core-shell structure 2 The polysulfone microsphere toughens the epoxy resin, the thermoplastic resin polysulfone and the rigid inorganic nano-particle SiO 2 Can improve the toughness of the epoxy resin and the inorganic nano particle SiO 2 Can also make up for the defects of resin rigidity reduction and the like caused by polysulfone addition, and simultaneously, the shell layer material polysulfone is used for preparing nano SiO of the core layer 2 The coating can prevent aggregation, and the polysulfone with the shell layer can also improve nano SiO due to the close structure of the polysulfone and the epoxy resin and high compatibility 2 Compatibility with epoxy resin, and the toughening effect on the epoxy resin is ensured.
Description
Technical Field
The invention belongs to the technical field of carbon fiber reinforced epoxy resin matrix composite materials, and particularly relates to a toughening modified epoxy resin composition, a composite material and a preparation method thereof.
Background
The carbon fiber reinforced epoxy resin based composite material is a composite material which is formed by taking epoxy resin as a matrix and taking carbon fiber or fabric thereof as a reinforcement. The composite material has the properties of light weight and high strength, and is widely applied to the fields of wind power industry, electronics and electricity, building industry, road traffic, chemical industry corrosion prevention, petrochemical industry, aerospace, ship transportation and the like, and the market demand of the composite material also shows a trend of increasing year by year. However, the epoxy resin forms a three-dimensional network structure after crosslinking and curing, the crosslinking density is increased, the internal stress is improved, and the cured product is hard and brittle, has poor toughness and is easy to crack, so that the application of the epoxy resin is limited.
At present, three approaches are mainly adopted to improve the toughness of the carbon fiber reinforced epoxy resin matrix composite, namely: the performance of the carbon fiber is improved, the fracture toughness of the epoxy resin matrix is improved, and the interfacial bonding performance between the reinforcing material and the epoxy resin matrix is improved. From the perspective of improving the fracture toughness of the epoxy resin matrix, the main method comprises the following steps: thermoplastic resin toughening, inorganic rigid nanoparticle toughening and rubber elastomer toughening. The thermoplastic resin toughening is to add high-strength, high-modulus and good-heat-resistance thermoplastic resin modified epoxy resin, the thermoplastic resin and the epoxy resin have similar chemical structures, the thermoplastic resin can be well compatible with the epoxy resin in the initial mixing stage of material preparation, induced phase separation can occur in the heating and curing process, the thermoplastic resin can improve the fracture toughness of the epoxy resin through mechanisms such as crack nail anchors, crack bridging, crack path deflection and the like, but the addition of the thermoplastic resin can reduce the tensile property, bending property and other mechanical properties of the epoxy resin, and the thermoplastic resin must be subjected to reaction induced phase separation to form a second phase, so that the problem that the toughening effect is greatly reduced due to incomplete phase separation exists. The inorganic rigid nano particle toughening is based on a crack riveting mechanism, the rigid nano particle and the epoxy resin form proper acting force, when the rigid particle deforms, a large amount of energy can be consumed to generate cracks, and meanwhile, silver grains in the epoxy resin solidified material are passivated when being expanded and meet the rigid particle, so that the expansion is blocked, the toughening effect is realized, the toughness of the epoxy resin can be improved, and the other mechanical properties of the epoxy resin can be improved. However, the surface energy of the nano inorganic rigid particles is high, agglomeration is easy to occur in the mixing process in the initial stage of preparation, the system is unevenly mixed, the toughening effect is poor, and the compatibility between the inorganic rigid particles and the epoxy resin is poor. The toughening of the rubber elastomer is realized by dispersing particles formed by rubber in epoxy resin, and separating out rubber phase during curing to induce silver streaks and shear bands so as to achieve the toughening effect. The rubber has obvious toughening effect, but can reduce the strength, rigidity and thermal stability of the epoxy resin.
Disclosure of Invention
The invention solves the technical problem of providing a toughened and modified epoxy resin composition, a composite material and a preparation method thereof, and SiO with a core-shell structure is added 2 The polysulfone microsphere toughens the epoxy resin, the thermoplastic resin polysulfone and the rigid inorganic nano-particle SiO 2 Can improve the toughness of the epoxy resin and the inorganic nano particle SiO 2 Can also make up for the reduction of other mechanical properties of the resin caused by polysulfone addition, and simultaneously, the shell layer material polysulfone is used for making the nano SiO of the core layer 2 The coating can prevent aggregation, and the polysulfone with the shell layer can also improve nano SiO due to the close structure of the polysulfone and the epoxy resin and high compatibility 2 Compatibility with epoxy resin, and the toughening effect on the epoxy resin is ensured.
In order to solve the above problems, a first aspect of the present invention provides a toughening modified epoxy resin composition:
the epoxy resin composition comprises the following components in parts by weight: 100 parts of epoxy resin and SiO with core-shell structure 2 2-20 parts of polysulfone microsphere and 20-25 parts of curing agent; siO of the core-shell structure 2 -polysulfone microsphere comprising a polysulfone shell and SiO encapsulated in the polysulfone shell 2 And (3) a core.
Preferably, the epoxy resin composition comprises, in parts by mass: 100 parts of epoxy resin and SiO with core-shell structure 2 8-12 parts of polysulfone microsphere and 20-25 parts of curing agent.
Preferably, the SiO of the core-shell structure 2 In polysulfone microspheres, siO 2 The mass ratio of the core to the polysulfone shell layer is 1: (2-5).
Preferably, the SiO of the core-shell structure 2 In polysulfone microspheres, siO 2 The mass ratio of the core to the polysulfone shell layer is 1: (3.5-4).
The second aspect of the invention provides a toughened and modified carbon fiber reinforced epoxy resin based composite material, comprising the toughened and modified epoxy resin composition and a carbon fiber reinforced material.
The third aspect of the present invention provides a method for preparing the toughening modified epoxy resin composition, comprising the following steps:
SiO of epoxy resin and core-shell structure 2 Mixing polysulfone microsphere and curing agent, and stirring uniformly to obtain the epoxy resin composition.
Preferably, the method specifically comprises the following steps:
heating epoxy resin to a flowing state, and heating SiO of the core-shell structure 2 Adding polysulfone microspheres into epoxy resin, stirring for 1-5h, then adding the curing agent, and stirring for 0.5-1h to obtain the epoxy resin composition.
Preferably, the SiO of the core-shell structure 2 The polysulphone microsphere is prepared by adopting a liquid-liquid phase conversion method, and specifically comprises the following steps: siO is made of 2 Adding into N, N-dimethylacetamide, dispersing to obtain SiO 2 A dispersion; polysulfone is then added to the SiO 2 Dispersing in the dispersion liquid to obtain a mixed liquid; then the mixed solution is injected into water for liquid-liquid phase separation to obtain the SiO with the core-shell structure 2 Polysulfone microspheres.
The fourth aspect of the invention provides a preparation method of the toughened and modified carbon fiber reinforced epoxy resin matrix composite material, which comprises the following steps:
s1, impregnating a carbon fiber reinforced material with the toughened and modified epoxy resin composition to obtain a prepreg;
s2, curing and forming the prepreg to obtain the toughened and modified carbon fiber reinforced epoxy resin matrix composite material.
Preferably, the curing system in the step S2 is as follows: heating at 100-120deg.C for 0.5-2 hr, then heating at 130-150deg.C for 3-6 hr, and then heating at 170-190 deg.C for 0.5-2 hr.
Compared with the prior art, the invention has the following beneficial effects:
the toughened and modified epoxy resin composition, the composite material and the preparation method thereof are added with SiO with a core-shell structure 2 The polysulfone microsphere is toughened, and the shell layer polysulfone material belongs to heatThe plastic resin has the advantages of high strength, high modulus and good heat resistance, can obviously improve the toughness of the epoxy resin composition, but can have adverse effects on other mechanical properties such as tensile property, bending property and the like of the epoxy resin, while the SiO of the core layer 2 The epoxy resin is inorganic rigid nano particles, and can improve mechanical properties such as tensile property, bending property and the like while improving the toughness of the epoxy resin; and due to nano SiO 2 High surface energy, easy agglomeration, and nano SiO of nuclear layer 2 After the particles are coated by the polysulfone shell layer, the aggregation among the particles can be prevented, the polysulfone shell layer has a similar structure with the epoxy resin, the compatibility is high, and the nano SiO is prepared 2 The coating is coated in the polysulfone shell layer, so that the compatibility of the polysulfone shell layer and the epoxy resin can be improved, and the toughening effect of the epoxy resin is ensured.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the method for improving the fracture toughness of the epoxy resin matrix, the thermoplastic resin is toughened to reduce the rigidity and other mechanical properties of the epoxy resin; the inorganic rigid nano particles can be toughened and the rigidity of the epoxy resin is improved, but the inorganic rigid nano particles are easy to agglomerate in the mixing process of the preparation, and the compatibility between the inorganic rigid particles and the epoxy resin is poor, so that the system is unevenly mixed; the rubber elastomer has obvious toughening effect, but can reduce the strength, rigidity and thermal stability of the epoxy resin.
In order to solve the above problems, a first aspect of an embodiment of the present invention provides a toughening modified epoxy resin composition, which includes, in parts by mass: 100 parts of epoxy resin and SiO with core-shell structure 2 2-20 parts of polysulfone microsphere and 20-25 parts of curing agent; siO of the core-shell structure 2 -polysulfone microsphere comprising a polysulfone shell and encapsulated in the polysulfone shellSiO in the shell layer 2 And (3) a core.
The toughened and modified epoxy resin composition of the embodiment of the invention is added with SiO with a core-shell structure 2 The polysulfone microsphere is toughened, the shell polysulfone material belongs to thermoplastic resin, has the advantages of high strength, high modulus and good heat resistance, can obviously improve the toughness of the epoxy resin composition, but can have adverse effects on other mechanical properties such as tensile property, bending property and the like of the epoxy resin, and the SiO of the core layer 2 The epoxy resin is inorganic rigid nano particles, and can improve mechanical properties such as tensile property, bending property and the like while improving the toughness of the epoxy resin; and due to nano SiO 2 High surface energy, easy agglomeration, and nano SiO of nuclear layer 2 After the particles are coated by the polysulfone shell layer, the aggregation among the particles can be prevented, the polysulfone shell layer has a similar structure with the epoxy resin, the compatibility is high, and the nano SiO is prepared 2 The coating is coated in the polysulfone shell layer, so that the compatibility of the polysulfone shell layer and the epoxy resin can be improved, and the toughening effect of the epoxy resin is ensured.
In some embodiments, the epoxy resin composition includes, in parts by weight: 100 parts of epoxy resin and SiO with core-shell structure 2 8-12 parts of polysulfone microsphere and 20-25 parts of curing agent. SiO of core-shell structure 2 The addition amount of the polysulfone microsphere is too small, the toughening effect is not obvious, and if the addition amount is too large, the dispersibility in the epoxy resin is poor, and the toughening effect is affected. The inventor experiment researches show that the epoxy resin has the best toughening effect and other mechanical properties by adopting the mass part ratio.
In some embodiments, the core-shell structured SiO 2 In polysulfone microspheres, siO 2 The mass ratio of the modified polysulfone is 1: (2-5). The polysulfone has remarkable effect of improving the toughness of the epoxy resin, but can reduce other mechanical properties of the epoxy resin, while SiO 2 Other mechanical properties are improved while improving the toughness of the epoxy resin, so that SiO is added into the epoxy resin 2 The mass content ratio of the epoxy resin to polysulfone can influence the toughening effect and other mechanical properties of the epoxy resin, and meanwhile, the nuclear layer SiO 2 The mass ratio of the core-shell polysulphone to the shell polysulphone also influences the performance of the microsphere with the core-shell structure, and the mass ratio of the core-shell polysulphone to the shell polysulphone is as followsOn the nuclear layer SiO 2 The mass ratio of the polysulfone with the shell layer directly influences the thickness of the formed shell layer, if the polysulfone content is too high, the shell layer is too thick, and the SiO of the core layer cannot be effectively exerted 2 The toughening effect of the catalyst is that the polysulfone content is too low, the shell layer is too thin, and the SiO of the core layer cannot be effectively coated 2 Thus, siO of core-shell structure 2 In polysulfone microspheres, siO 2 The effect of mass ratio to polysulfone on the toughening effect of epoxy resins is complex. The inventor tries to find out that when the mass ratio is adopted, the toughening effect of the epoxy resin is optimal, and other mechanical properties are better.
In some embodiments, the core-shell structured SiO 2 In polysulfone microspheres, siO 2 The mass ratio to polysulfone is preferably 1: (3.5-4).
In some embodiments, the core-shell structured SiO 2 In polysulfone microspheres, siO 2 The mass ratio to polysulfone is further preferably 1:3.8.
in some embodiments, the epoxy resin may be one or a combination of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin.
In some embodiments, the curing agent may be at least one of an amine curing agent, a polyamide curing agent, an anhydride curing agent, an alcohol curing agent, an imidazole curing agent.
The second aspect of the invention provides a toughened and modified carbon fiber reinforced epoxy resin based composite material, comprising the toughened and modified epoxy resin composition and a carbon fiber reinforced material.
In some embodiments, the mass ratio of carbon fiber reinforcement in the composite is 20% -40%, preferably 30%.
The third aspect of the present invention provides a method for preparing the toughening modified epoxy resin composition, comprising the following steps:
SiO of epoxy resin and core-shell structure 2 Mixing polysulfone microsphere and curing agent, and stirring uniformly to obtain the epoxy resin composition.
In some embodiments, the method specifically comprises the following steps:
heating epoxy resin to a flowing state, and heating SiO of the core-shell structure 2 Adding polysulfone microspheres into epoxy resin, stirring for 1-5h, then adding the curing agent, and stirring for 0.5-1h to obtain the epoxy resin composition.
In some embodiments, the core-shell structured SiO 2 The polysulphone microspheres can be prepared by various methods for preparing microspheres with core-shell structures which are currently available. For example, emulsion synthesis, self-assembly, phase inversion, and the like can be used. In some embodiments, the core-shell structured SiO 2 The polysulphone microsphere is prepared by adopting a liquid-liquid phase conversion method, and specifically comprises the following steps: siO is made of 2 Adding into N, N-dimethylacetamide, dispersing to obtain SiO 2 A dispersion; polysulfone is then added to the SiO 2 Dispersing in the dispersion liquid to obtain a mixed liquid; then the mixed solution is injected into water for liquid-liquid phase separation to obtain the SiO with the core-shell structure 2 Polysulfone microspheres. Adding the mixed solution into polysulfone non-solvent water, exchanging the non-solvent with the solvent in the polymer solution drop to make the polymer solution undergo the process of liquid-liquid phase separation to form high-molecular concentrated phase and dilute phase, then gradually extracting solvent in the high-molecular concentrated phase, and finally forming ball with SiO only 2 And polysulfone.
The fourth aspect of the invention provides a preparation method of the toughened and modified carbon fiber reinforced epoxy resin matrix composite material, which comprises the following steps:
s1, impregnating a carbon fiber reinforced material with the toughened and modified epoxy resin composition to obtain a prepreg;
s2, curing and forming the prepreg to obtain the toughened and modified carbon fiber reinforced epoxy resin matrix composite material.
In some embodiments, the preparation method further comprises, before step S1: and (3) vacuumizing and defoaming the epoxy resin composition at 50 ℃ for 30min.
In some embodiments, the curing schedule in step S2 is: heating at 100-120deg.C for 0.5-2 hr, then heating at 130-150deg.C for 3-6 hr, and then heating at 170-190 deg.C for 0.5-2 hr.
The curing system has a larger influence on the phase separation process of the thermoplastic resin polysulfone and the epoxy resin, the viscosity of the epoxy resin is low when the curing is started, the compatibility of the polysulfone and the epoxy resin is better, and the phase separation is less; as the curing reaction proceeds, the relative molecular mass of the epoxy resin gradually increases, the compatibility between the components decreases, phase separation occurs, and in the latter stage of curing, the molecular diffusion movement is restricted due to the formation of a crosslinked network, so that the development of phase separation is suppressed. If the curing temperature is lower, the phase separation occurs later, and when the curing temperature is high, the phase separation speed of the two phases is increased, the phase separation is relatively complete before reaching the gel point, and the cross-linked network formed by epoxy after the gel point cannot inhibit the reverse expansion of the phase separation. Therefore, the degree of phase separation of the cured epoxy resin can be regulated and controlled by regulating the relative speed of the curing reaction and the phase separation, so that the toughening effect of the epoxy resin is improved. The inventor finds that the phase separation is more complete and the toughening effect of the composite material is optimal by experimental trial and research when the curing parameters are adopted.
Example 1
The preparation method of the toughening modified epoxy resin composition comprises the following steps:
(1) Preparation of SiO of core-shell structure 2 Polysulphone microsphere, siO 2 Adding into N, N-dimethylacetamide, dispersing by ultrasonic wave to obtain SiO 2 A dispersion; polysulfone is then added to the SiO 2 Dispersing in the dispersion liquid by ultrasonic to obtain a mixed liquid; then instilling the mixed solution into the secondary distilled water by a dropper, and performing liquid-liquid phase separation to obtain the SiO with the core-shell structure 2 Polysulfone microspheres, after which the microspheres are thoroughly washed with distilled water, the solvent is removed and preserved for further use, wherein SiO 2 The mass ratio of the modified starch to polysulfone is 1:3.8.
(2) Bisphenol A epoxy resin is heated to a flowing state, and 10 parts by mass of SiO with a core-shell structure is added 2 Polysulfone microspheres were added to 100 parts by mass of epoxy resin and stirred for 3 hours, followed by 25 parts by mass of polyamide curing agent and stirredStirring for 1h to obtain the epoxy resin composition.
The preparation method of the carbon fiber reinforced epoxy resin matrix composite material by adopting the obtained epoxy resin composition comprises the following steps:
(1) Vacuumizing and defoaming the obtained epoxy resin composition at 50 ℃ for 30min;
(2) Impregnating a carbon fiber reinforced material with the toughened and modified epoxy resin composition to obtain a prepreg;
(3) Paving the prepreg in a mould, pouring the epoxy resin composition in vacuum, and curing and forming, wherein the curing system is as follows: heating at 110 ℃ for 1h, then heating at 140 ℃ for 5h, and then heating at 180 ℃ for 1h to obtain the toughened and modified carbon fiber reinforced epoxy resin-based composite material, wherein the mass percentage of epoxy resin in the composite material is 70%.
Example 2
The preparation methods of the toughening-modified epoxy resin composition and the composite material in this example are the same as those in example 1, except that the epoxy resin composition comprises: 100 parts by mass of epoxy resin and 8 parts by mass of SiO with core-shell structure 2 Polysulfone microspheres, 20 parts by mass of polyamide curing agent.
Example 3
The preparation methods of the toughening-modified epoxy resin composition and the composite material in this example are the same as those in example 1, except that the epoxy resin composition comprises: 100 parts by mass of epoxy resin and 12 parts by mass of SiO with core-shell structure 2 Polysulfone microspheres, 20 parts by mass of polyamide curing agent.
Example 4
The preparation methods of the toughening-modified epoxy resin composition and the composite material in this example are the same as those in example 1, except that the epoxy resin composition comprises: 100 parts by mass of epoxy resin and 5 parts by mass of SiO with core-shell structure 2 Polysulfone microspheres, 25 parts by mass of polyamide curing agent.
Example 5
The preparation method of the toughening modified epoxy resin composition and the composite material and the actual implementation methodExample 1 was the same as example 1 except that the epoxy resin composition contained: 100 parts by mass of epoxy resin and 15 parts by mass of SiO with core-shell structure 2 Polysulfone microspheres, 20 parts by mass of polyamide curing agent.
Example 6
The preparation methods of the toughening modified epoxy resin composition and the composite material in the embodiment are the same as those in the embodiment 1, and are different from those in the SiO with the core-shell structure 2 In polysulfone microspheres, siO 2 The mass ratio of the modified starch to the polysulfone microsphere is 1:3.5.
Example 7
The preparation methods of the toughening modified epoxy resin composition and the composite material in the embodiment are the same as those in the embodiment 1, and are different from those in the SiO with the core-shell structure 2 In polysulfone microspheres, siO 2 The mass ratio of the modified polyvinyl alcohol to the polysulfone microspheres is 1:4.
Example 8
The preparation methods of the toughening modified epoxy resin composition and the composite material in the embodiment are the same as those in the embodiment 1, and are different from those in the SiO with the core-shell structure 2 In polysulfone microspheres, siO 2 The mass ratio of the modified polymer to the polysulfone microsphere is 1:2.5.
Example 9
The preparation methods of the toughening modified epoxy resin composition and the composite material in the embodiment are the same as those in the embodiment 1, and are different from those in the SiO with the core-shell structure 2 In polysulfone microspheres, siO 2 The mass ratio of the modified polyvinyl alcohol to the polysulfone microspheres is 1:5.
Example 10
The preparation method of the toughening modified epoxy resin composition and the composite material in the embodiment has the same steps and raw material proportions as those in the embodiment 1, and the difference is that the curing system in the step S2 during curing and forming is as follows: heating at 80℃for 1h, then at 120℃for 5h, and then at 160℃for 1h.
Example 11
The preparation method of the toughening modified epoxy resin composition and the composite material in the embodiment has the same steps and raw material proportions as those in the embodiment 1, and the difference is that the curing system in the step S2 during curing and forming is as follows: heating at 130 ℃ for 1h, then at 160 ℃ for 5h, and then at 200 ℃ for 1h.
Comparative example 1
The epoxy resin composition of this comparative example uses individual nano SiO 2 The microparticle is toughened, and the preparation method of the epoxy resin composition comprises the following steps:
bisphenol A epoxy resin is heated to a flowing state, and 10 parts by mass of nano SiO is added 2 100 parts by mass of bisphenol A type epoxy resin was added and stirred for 3 hours, and then 25 parts by mass of polyamide curing agent was added and stirred for 1 hour to obtain an epoxy resin composition.
The preparation method of the carbon fiber reinforced epoxy resin matrix composite of this example is the same as that of example 1.
Comparative example 2
The epoxy resin composition of the comparative example is toughened by adopting independent polysulfone, and the preparation method of the epoxy resin composition comprises the following steps:
the bisphenol a type epoxy resin was heated to a flowing state, 10 parts by mass of polysulfone was added to 100 parts by mass of the bisphenol a type epoxy resin and stirred for 3 hours, then 25 parts by mass of the polyamide curing agent was added and stirred for 1 hour to obtain an epoxy resin composition.
The preparation method of the carbon fiber reinforced epoxy resin matrix composite of this example is the same as that of example 1.
Comparative example 3
The epoxy resin composition of the comparative example adopts nano SiO 2 The microparticle and polysulfone are toughened together, and the preparation method of the epoxy resin composition comprises the following steps:
bisphenol A epoxy resin was heated to a fluidized state, and 2.1 parts by mass of nano SiO 2 7.9 parts by mass of polysulfone was added to 100 parts by mass of bisphenol A type epoxy resin and stirred for 3 hours, and then 25 parts by mass of polyamide curing agent was added and stirred for 1 hour to obtain an epoxy resin composition.
The preparation method of the carbon fiber reinforced epoxy resin matrix composite of this example is the same as that of example 1.
Performance test of carbon fiber reinforced epoxy resin matrix composite
The carbon fiber reinforced epoxy resin matrix composite materials obtained in the examples and the comparative examples were subjected to fracture toughness test and bending performance test. The interlayer shear performance test method refers to JC/T773-96; interlayer fracture toughness test is referred to HB7402-96 standard; bending performance test is described in GB3356-1999, using a short strut three point load. The test results are shown in Table 1 below. As can be seen from the data in the following table, the carbon fiber reinforced epoxy resin based composite material of the present invention is superior to the individual SiO of comparative examples 1, 2 and 3 2 Toughening, individual polysulfone toughening and SiO 2 Polysulphone is mixed and toughened by adding SiO with core-shell structure 2 The polysulfone microspheres significantly improve the toughness, tensile property and bending property of the composite material, wherein the mass parts of the components in the embodiments 1-3 are in the preferred ranges, and when the mass parts are in the ranges, the composite material has better mechanical comprehensive properties compared with the embodiments 4 and 5; siO of examples 1, 6 and 7 2 The mass ratio to polysulfone is in the preferred range, where the composite has better mechanical properties than examples 8, 9.
TABLE 1
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (5)
1. A toughened and modified epoxy resin composition characterized by:
the epoxy resin composition comprises the following components in parts by weight: 100 parts of epoxy resin and SiO with core-shell structure 2 8-12 parts of polysulfone microsphere and 20-25 parts of curing agent; the core-shell knotStructural SiO 2 -polysulfone microsphere comprising a polysulfone shell and SiO encapsulated in the polysulfone shell 2 A core; siO of the core-shell structure 2 In polysulfone microspheres, siO 2 The mass ratio of the core to the polysulfone shell layer is 1: (3.5-4);
the preparation method of the toughening modified epoxy resin composition comprises the following steps:
SiO of epoxy resin and core-shell structure 2 Mixing polysulfone microspheres and a curing agent, and uniformly stirring to obtain an epoxy resin composition; wherein, the SiO of the core-shell structure 2 The polysulphone microsphere is prepared by adopting a liquid-liquid phase conversion method, and specifically comprises the following steps: siO is made of 2 Adding into N, N-dimethylacetamide, dispersing to obtain SiO 2 A dispersion; polysulfone is then added to the SiO 2 Dispersing in the dispersion liquid to obtain a mixed liquid; then the mixed solution is injected into water for liquid-liquid phase separation to obtain the SiO with the core-shell structure 2 Polysulfone microspheres.
2. The toughening modified epoxy resin composition according to claim 1, wherein the preparation method of the toughening modified epoxy resin composition specifically comprises the following steps:
heating epoxy resin to a flowing state, and heating SiO of the core-shell structure 2 Adding polysulfone microspheres into epoxy resin, stirring for 1-5h, then adding the curing agent, and stirring for 0.5-1h to obtain the epoxy resin composition.
3. A toughened and modified carbon fiber reinforced epoxy resin matrix composite material is characterized in that:
comprising the toughening modified epoxy resin composition according to claim 1 or 2 and a carbon fiber reinforced material.
4. A method of preparing the toughened and modified carbon fiber reinforced epoxy resin based composite material of claim 3, comprising the steps of:
s1, impregnating a carbon fiber reinforced material with the toughening modified epoxy resin composition according to claim 1 or 2 to obtain a prepreg;
s2, curing and forming the prepreg to obtain the toughened and modified carbon fiber reinforced epoxy resin matrix composite material.
5. The method of manufacturing according to claim 4, wherein:
the curing system in the step S2 is as follows: heating at 100-120deg.C for 0.5-2 hr, then heating at 130-150deg.C for 3-6 hr, and then heating at 170-190 deg.C for 0.5-2 hr.
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