CN113246564A - High-strength high-toughness phthalonitrile-based composite material and preparation method and application thereof - Google Patents
High-strength high-toughness phthalonitrile-based composite material and preparation method and application thereof Download PDFInfo
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- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims abstract description 119
- 239000002131 composite material Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 117
- 239000011347 resin Substances 0.000 claims abstract description 117
- 239000002245 particle Substances 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000011229 interlayer Substances 0.000 claims abstract description 35
- 239000010410 layer Substances 0.000 claims abstract description 23
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 13
- 239000010954 inorganic particle Substances 0.000 claims abstract description 12
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 7
- 238000011417 postcuring Methods 0.000 claims description 26
- 229910000831 Steel Inorganic materials 0.000 claims description 21
- 239000010959 steel Substances 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 19
- 239000004744 fabric Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 10
- 229920002530 polyetherether ketone Polymers 0.000 claims description 10
- 239000012783 reinforcing fiber Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 230000009477 glass transition Effects 0.000 claims description 7
- 229920006260 polyaryletherketone Polymers 0.000 claims description 7
- 229920006259 thermoplastic polyimide Polymers 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 239000004416 thermosoftening plastic Substances 0.000 claims description 6
- 229910052580 B4C Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920002577 polybenzoxazole Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 13
- 230000009471 action Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 38
- 238000012360 testing method Methods 0.000 description 36
- 239000000843 powder Substances 0.000 description 26
- 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 20
- 239000012745 toughening agent Substances 0.000 description 20
- 238000005520 cutting process Methods 0.000 description 18
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- 239000007787 solid Substances 0.000 description 16
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- 229920000049 Carbon (fiber) Polymers 0.000 description 11
- 239000004917 carbon fiber Substances 0.000 description 11
- IHCNWWQQHZNTSG-UHFFFAOYSA-N 3-aminobenzene-1,2-dicarbonitrile Chemical compound NC1=CC=CC(C#N)=C1C#N IHCNWWQQHZNTSG-UHFFFAOYSA-N 0.000 description 10
- 238000005452 bending Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 238000009966 trimming Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical class C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
- B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B64—AIRCRAFT; AVIATION; COSMONAUTICS
- B64G—COSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
- B64G1/00—Cosmonautic vehicles
- B64G1/22—Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
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- 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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Abstract
The invention discloses a high-strength high-toughness phthalonitrile-based composite material and a preparation method and application thereof. The composite material comprises a plurality of substrate layers in a stack, each substrate layer comprising a fiber reinforced phthalonitrile resin; the composite material further comprises at least one interlayer region, each interlayer region is formed between two adjacent matrix layers, and each interlayer region contains toughening particles, wherein the toughening particles are selected from thermoplastic resin particles and/or inorganic particles. According to the invention, by means of the method of directionally introducing the toughening particle component into the interlayer region, the excellent heat resistance of the phthalonitrile composite material is maintained to the greatest extent, the fracture toughness of the phthalonitrile composite material is greatly improved, the rapid damage of the interlayer interface region under the action of load is limited, and the original mechanical strength of the composite material is ensured or improved, so that the purpose of toughening and reinforcing is achieved at the same time. The composite material can be applied to the field of aerospace high-temperature-resistant structure composite materials.
Description
Technical Field
The invention belongs to the field of resin matrix composite material manufacturing, and particularly relates to a high-strength high-toughness phthalonitrile-based composite material as well as a preparation method and application thereof.
Background
With the vigorous development of the aerospace field, the manufacturing technology puts higher requirements on the light weight and high performance of the material. The fiber reinforced resin matrix composite material has been widely used in the aerospace field due to its excellent characteristics of high specific strength, specific stiffness, designability, easy integral forming and the like. The resin matrix of the fiber composite material can be divided into thermoplastic resin and thermosetting resin, and common thermosetting resin systems mainly comprise epoxy resin and bismaleimide resin systems suitable for medium-low temperature environments and polyimide resin and phthalonitrile resin systems suitable for high-temperature environments above 400 ℃.
The phthalonitrile resin is a novel thermosetting resin system with a phthalonitrile group as a crosslinking structure, and a monomer or oligomer with a phthalonitrile end group can be crosslinked and cured under the action of an active hydrogen catalyst such as arylamine and the like to obtain corresponding resin. The phthalonitrile resin has excellent thermal stability, high carbon residue rate, high glass transition temperature, low water absorption and low volume shrinkage, and the composite material taking the phthalonitrile resin as a matrix also has excellent mechanical property and thermal oxidation stability. The superior performance of the phthalonitrile resin comes from a large number of aromatic heterocyclic structures formed after the high crosslinking and curing of a terminal phthalonitrile group, such as phthalocyanine ring, triazine ring and the like. The aromatic heterocyclic structures can resist the combined action of high temperature and oxygen, so that the phthalonitrile resin has a glass transition temperature higher than 450 ℃, and the resin also has excellent ablation resistance and flame retardant property.
However, compared with polyimide-based composite materials, the phthalonitrile-based composite materials have poor interlayer bonding performance, and the cross-linked network has large curing stress due to the high cross-linked density of resin, which is reflected by macroscopic high brittleness. Taking T700 unidirectional carbon fiber reinforced phthalonitrile-based composite material as an example, the interlaminar shear strength of the composite material is about 40MPa, which is far lower than that of polyimide-based composite material with the same heat-resistant grade. In addition, as the triazine ring and the phthalocyanine ring formed after the phthalonitrile group is crosslinked are rigid large aromatic rings, the crosslinked structure is difficult to move freely, and the entanglement and infiltration between the matrix and the reinforced fiber are greatly limited, namely, the strength of an interface phase formed between phthalonitrile resin and the fiber is weak, the interface phase is easy to damage when cracks are expanded, and the original excellent mechanical properties of the fiber and the resin are difficult to exert.
In order to solve the problem, researchers at home and abroad carry out corresponding research on the reinforcing, toughening and modifying work of the phthalonitrile-based composite material. The method adopted at the present stage mainly comprises two methods, one is to design the structure of phthalonitrile monomer or oligomer, and to introduce a molecular chain segment with certain length and flexibility between the end-capped phthalonitrile groups, so as to improve the motion capability of the molecular chain and the wetting property on the fiber surface, thereby improving the toughness and the strength of the resin. Hydroxyl-and nitrile-terminated polyetheretherketone PEEK oligomers were prepared in 2015 by Augustine D, Mathew D, Reghunadhan Nair C. Polymer International,2015,64(1): 146-. However, this method is inconsistent with the background of using phthalonitrile resin as a heat-resistant structural material, i.e. the mechanical properties are improved and the heat-resistant properties of the resin are lost, and as in the aforementioned research, the heat-resistant properties of the cured resin after introducing the flexible PEEK segment are reduced to some extent. At present, another main method for reinforcing, toughening and modifying the phthalonitrile composite material is to blend and modify phthalonitrile resin and other thermoplastic resin or elastomer with relatively good toughness. In 2016, carboxyl-terminated nitrile rubber is introduced into a phthalonitrile resin system by a blending means, and the bending strength is improved from 528MPa to 534 MPa. However, the heat resistance of the carboxyl-terminated nitrile rubber adopted by blending is far lower than that of phthalonitrile resin, so that the 5% thermal decomposition temperature of a blending system in nitrogen is reduced from 567 ℃ to 509 ℃, and the heat resistance of the system is reduced, which is not favorable for the resin matrix of the high-temperature-resistant structural composite material.
In summary, the existing reinforcing and toughening measures of the phthalonitrile-based composite material are mainly focused on modification of the resin matrix layer, i.e., a molecular chain segment with good flexibility is introduced into a main chain structure, or a large amount of elastomer or thermoplastic resin with good toughness or wettability is introduced into a matrix with poor toughness in a blending mode, so that the toughness of a resin system and the corresponding composite material is improved to a certain extent, and the mechanical strength of the composite material is improved by improving the wettability of fiber and resin. However, such methods still have significant drawbacks: first, problem of heat resistance: the toughened and reinforced structure or component with good toughness but poor heat resistance causes the overall reduction of the heat resistance of the modified resin system; secondly, the process problem is as follows: the introduction of thermoplastic resin or elastomer improves the viscosity of the system, so that the processing and forming are difficult; thirdly, the inherent characteristics of the composite material: that is, due to the constraint effect of the reinforcing fibers, the resin performance is difficult to be fully reflected as the performance of the composite material, and the toughness and strength of the composite material are improved to a limited extent.
Disclosure of Invention
The invention provides a phthalonitrile-based composite material, which has high strength and high toughness, and comprises a plurality of matrix layers in a stacking form, wherein each matrix layer comprises fiber-reinforced phthalonitrile resin;
the composite material further comprises at least one interlayer region, each interlayer region is formed between two adjacent matrix layers, and each interlayer region contains toughening particles selected from thermoplastic resin particles and/or inorganic particles.
According to the present invention, the thermoplastic resin particles may be selected from thermoplastic particles having a glass transition temperature higher than 250 ℃, such as at least one of thermoplastic polyimide, polyetheretherketone, polyaryletherketone, modified polyaryletherketone (e.g., zwitterionic group-modified phenolphthalein type polyaryletherketone, abbreviated as PEK-C), polyetherimide, polybenzimidazole, polybenzoxazole, polyethersulfone, and the like; preferably a thermoplastic polyimide, polyetheretherketone and/or a modified polyaryletherketone (e.g. PEK-C).
According to the present invention, the inorganic particles may be selected from inorganic particles having high heat resistance, such as at least one of boron carbide, silicon carbide, boron nitride, alumina, and the like; preferably at least one of boron carbide, silicon carbide and boron nitride.
According to the invention, the toughening particles have an average particle size of not more than 30 μm, preferably not more than 20 μm, exemplary 3 μm, 5 μm, 10 μm, 30 μm.
According to the present invention, the phthalonitrile resin may be at least one selected from the group consisting of primary phthalonitrile resins (which are obtained by curing a small-molecule monomer containing a phthalonitrile group with the action of a curing agent), secondary phthalonitrile resins (which contain a molecular segment terminated with a phthalonitrile group), and other resins having a phthalonitrile group and having it as a crosslinking site; preferably a primary phthalonitrile resin.
For example, the small molecule monomer containing a phthalonitrile group has a structure as shown in formula (1):
wherein R is selected from any one of the following structures:
preferably, R is selected from any one of the following structures:
for example, the curing agent may be selected from substances having a phthalonitrile group containing an amino group and/or a hydroxyl group; preferably a substance having a phthalonitrile group containing an amino group; illustratively, the structure of the substance having a phthalonitrile group and containing an amino group may be represented by formula (2):
for example, the first generation phthalonitrile resin may be selected from at least one of the compounds represented by the formula (a) and the formula (b):
according to the invention, the reinforcing fibers are continuous fibers, and can be selected from single fiber fabrics or mixed fabrics of carbon fibers, glass fibers, quartz fibers and aramid fibers. Further, the fabric may be a unidirectional fabric or a two-dimensional fabric. An example is a carbon fiber unidirectional cloth.
According to the present invention, the interlayer region has a sea-island structure including the phthalonitrile resin and the toughening particles. The toughening particles are insoluble or incompletely soluble in the phthalonitrile resin. Further, the sea-island structure has a phase dimension of 1 to 50 μm, preferably 1 to 30 μm, and more preferably 5 to 20 μm.
According to the invention, the toughening particles account for 5-60%, preferably 5-50%, more preferably 10-35% of the mass of the phthalonitrile resin; illustratively, it accounts for 5%, 10%, 12.5%, 15%, 20% of the mass of the phthalonitrile resin.
According to the invention, the glass transition temperature of the composite material is above 420 ℃, for example at a temperature of 435-.
According to the invention, the flexural strength of the composite material is higher than 1400MPa, for example 1450-1800MPa, and exemplarily 1494MPa, 1584MPa, 1598MPa, 1599MPa, 1673MPa, 1678MPa, 1692 MPa.
According to the invention, the flexural modulus of the composite material is greater than 90GPa, for example 92-110GPa, and exemplarily 93.4GPa, 96.0GPa, 96.8GPa, 98.5GPa, 102GPa, 103GPa, 104 GPa.
According to the invention, the interlaminar shear strength of the composite is not less than 50MPa, for example 50-80MPa, illustratively 50.5MPa, 51.0MPa, 58.0MPa, 63.0MPa, 64.5MPa, 65.1MPa, 70.2 MPa.
The invention also provides a preparation method of the phthalonitrile-based composite material, which comprises the following steps:
(1) preparing a resin prepreg containing phthalonitrile resin and reinforcing fibers;
(2) attaching toughening particles to the surface of the resin prepreg to obtain a toughened phthalonitrile resin prepreg;
(3) and (3) paving the toughened phthalonitrile resin prepreg in the step (2) to obtain a prefabricated body, and curing the prefabricated body to obtain the phthalonitrile-based composite material.
According to the preparation method of the present invention, the phthalonitrile resin, the reinforcing fibers and the toughening particles have the meanings and proportions as described above.
According to the preparation method, in the step (1), the phthalonitrile resin is prepared from a phthalonitrile resin monomer and a curing agent. For example, the mass ratio of the phthalonitrile resin monomer to the curing agent is (85-95): 5-15, preferably 95: 5.
According to the preparation method of the invention, in the step (1), the mass ratio of the phthalonitrile resin to the reinforcing fibers is 1 (1-1.5), for example, 1 (1-1.3), and the exemplary ratio is 1: 1.07.
According to the production method of the present invention, in step (1), the resin prepreg may be prepared by a solvent method or a melt method, and preferably by a solvent method. The solvent used in the solvent method is at least one of acetone, Dimethylformamide (DMF), dimethylacetamide (DMAc), Dimethylsulfoxide (DMSO), methylpyrrolidone (NMP), Tetrahydrofuran (THF), and the like. Illustratively, a phthalonitrile resin may be dissolved in acetone, and the resulting clear and homogeneous phthalonitrile/acetone solution used to impregnate the reinforcing fibers, resulting in the resin prepreg.
According to the preparation method provided by the invention, in the step (2), when the toughening particles are introduced, a certain spreadability of the resin prepreg is ensured.
The method for preparing the laminate according to the present invention, step (3), the form of the laminate is not limited, and the laminate known in the art may be used, for example, according to [0 ]]8The layering sequence of (1).
According to the preparation method of the invention, in the step (3), the curing comprises pre-curing and post-curing, and preferably, the preform is pre-cured in a vacuum bag or a steel mold and then transferred to an oven for post-curing. Wherein the pre-curing conditions comprise a treatment at 180 ℃ to 300 ℃ for 0.5 to 6h, for example at 200 ℃ to 280 ℃ for 0.5 to 5h, and exemplary pre-curing procedures comprise: curing at 200 deg.C for 0.5 hr, curing at 250 deg.C for 2 hr, and curing at 280 deg.C for 2 hr. Wherein the post-curing conditions comprise a treatment at 280 ℃ to 400 ℃ for 1 to 10 hours, for example at 300 ℃ to 380 ℃ for 1 to 6 hours, and illustratively the post-curing procedure comprises the following sequential curing treatments: curing at 315 deg.C for 4 hr, and curing at 375 deg.C for 2 hr. Further, the pre-curing is a hot pressing process with a pressure of 3-7MPa, such as 4-6MPa, exemplary 5 MPa.
According to an embodiment of the present invention, the method for preparing a phthalonitrile-based composite material comprises:
(1) pre-dipping phthalonitrile resin and reinforcing fiber to prepare resin prepreg, wherein the mass ratio of the phthalonitrile resin to the reinforcing fiber is 1 (1-1.5);
(2) uniformly loading toughening particles in the resin prepreg to obtain a particle-toughened phthalonitrile resin prepreg;
(3) paving the particle-toughened phthalonitrile resin prepreg in the step (2) to obtain a prefabricated body; and placing the prefabricated body in a vacuum bag or a steel mould for hot-pressing pre-curing, transferring the prefabricated body to an oven for post-curing, and finishing curing to obtain the phthalonitrile-based composite material.
The invention also provides the phthalonitrile-based composite material prepared by the method. In particular, the composite material has high strength and high toughness.
Further, the invention provides an application of the phthalonitrile-based composite material in aerospace high-temperature-resistant materials.
The invention has the beneficial effects that:
aiming at the current situations of poor toughness and low strength of the fiber reinforced phthalonitrile-based composite material and the defects of toughening and reinforcing means of the existing phthalonitrile-based composite material, the invention firstly introduces an interlayer toughening method into phthalonitrile resin which is thermosetting resin, and provides a high-strength high-toughness phthalonitrile-based composite material prepared by introducing toughening particles into interlayer weak links, a preparation method and application thereof.
(1) The preparation method provided by the invention utilizes the thermoplastic resin particles or the inorganic particles as the interlayer toughening material, limits crack propagation in the composite material damage process through the anchoring effect and yield effect of the interlayer particles, and slows down or avoids the damage process of the phthalonitrile-based composite material under the action of external force, thereby achieving the effect of toughening the phthalonitrile-based composite material. From the view of interlaminar shear strength, the amplitude of the composite material is improved by more than 40 percent compared with the prior art, which shows that the toughness of the composite material is obviously improved.
(2) The preparation method provided by the invention is based on the toughening mode of interlayer particles, the interlayer particles do not need to introduce a large amount of toughening components for toughening, and thermoplastic particles or inorganic particles with the mass fraction of 30% have no obvious influence on the viscosity of a phthalonitrile resin system, namely, the toughness performance is greatly improved by less particle loading, the interface continuity of the composite material and the resin fluidity in the vertical direction can be kept, and the influence on a forming process is small.
(3) In the preparation method provided by the invention, the toughening component is selected from thermoplastic particles with the glass transition temperature higher than 250 ℃ or inorganic particles with excellent heat resistance, so that the excellent heat resistance of the original phthalonitrile resin is ensured, and the phthalonitrile resin can be used as a high-temperature-resistant structural composite material resin matrix.
In conclusion, the method for directionally introducing the toughening particle component into the interlayer region can greatly improve the fracture toughness of the phthalonitrile composite while keeping the excellent heat resistance of the phthalonitrile composite to the maximum extent, limit the rapid damage of the interlayer interface region under the action of load, possibly further improve the strength on the basis of not influencing the strength of the composite, and simultaneously achieve the aim of toughening and reinforcing, thereby achieving the aim of improving the overall performance of the composite.
Drawings
FIG. 1 is a schematic representation of the preparation of interlaminar particle toughened phthalonitrile prepregs of example 1.
FIG. 2 is a distribution diagram of interlaminar particles obtained in example 1 in a high-strength and high-toughness phthalonitrile-based composite material.
FIG. 3 is a sea-island phase morphology (scale: 50 μm) of the interlayer region of the high strength and high toughness phthalonitrile-based composite material obtained in example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The structure of the aminophthalonitrile curing agent used in the examples and comparative examples is as follows:
the structures of the bisphenol A type phthalonitrile monomers used in the examples and comparative examples are as follows:
example 1
And mixing the bisphenol A type phthalonitrile resin monomer and the amino phthalonitrile curing agent powder according to the mass ratio of 95:5 to obtain the resin powder. And then heating and blending the resin powder and acetone at a mass ratio of 1:4 at 70 ℃ to dissolve the powder in the acetone to form a clear and uniform PN solution. Preparing a wet prepreg by using a PN solution with a solid content of 30g and 32g T700 carbon fiber unidirectional cloth, and introducing a thermoplastic particle toughening agent into an interlayer region when the prepreg still has certain spreadability: thermoplastic Polyimide (PI) particles with the particle size of 10 mu m, wherein the addition amount of the toughening agent is introduced according to the mass ratio of the solid content of the resin to the toughening agent of 90: 10.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedures are 200 ℃/0.5h, 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. And after post-curing is finished, cooling the composite material to room temperature along with the furnace, and taking out the composite material to obtain the 10 wt% PI modified high-strength high-toughness phthalonitrile-based composite material.
The preparation process of the phthalonitrile-based composite material is as shown in fig. 1, wherein toughening particles are loaded on a phthalonitrile resin prepreg, and a plurality of substrate layers in a stacking form are finally formed, each substrate layer comprises continuous fiber reinforced phthalonitrile resin and at least one interlayer region, each interlayer region is formed between two adjacent substrate layers, and each interlayer region comprises the toughening particles and the phthalonitrile resin.
FIG. 2 is a distribution diagram of interlayer particles in a phthalonitrile composite material, and toughening particles are insoluble or incompletely soluble in a phthalonitrile resin matrix layer, so that a sea-island phase structure (a sea-island phase structure is marked in a circle in FIG. 2) in an interlayer region shown in FIG. 3 is formed, and the phase dimension is controlled by the particle size of the toughening particles and is 5-20 μm.
The composite material obtained in this example was subjected to the following performance tests:
cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 1.
Performance of PI modified high-strength high-toughness phthalonitrile-based composite material with weight percent of 110% in table
Example 2
After bisphenol A type phthalonitrile resin monomer and amino phthalonitrile curing agent powder are mixed according to the mass ratio of 95:5, the resin powder and acetone are heated and blended at the temperature of 70 ℃ according to the mass ratio of 1:4, and the powder is dissolved in the acetone to form clear and uniform PN solution.
Preparing a wet prepreg by using a PN solution with a solid content of 30g and 32g T700 carbon fiber unidirectional cloth, and introducing a thermoplastic particle toughening agent into an interlayer region when the prepreg still has certain spreadability: modified polyaryletherketone (PEK-C) particles with the particle size of 10 mu m are introduced according to the mass ratio of the solid content of the resin to the toughening agent of 90: 10.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedures are 200 ℃/0.5h, 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. And after post-curing, cooling the composite material to room temperature along with the furnace, and taking out the composite material to obtain the 10 wt% PEK-C modified high-strength high-toughness phthalonitrile-based composite material.
Cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 2.
Performance of PEK-C modified high-strength and high-toughness phthalonitrile-based composite material with 210 wt% in table
Example 3
After bisphenol A type phthalonitrile resin monomer and amino phthalonitrile curing agent powder are mixed according to the mass ratio of 95:5, the resin powder and acetone are heated and blended at the temperature of 70 ℃ according to the mass ratio of 1:4, and the powder is dissolved in the acetone to form clear and uniform PN solution.
Preparing a wet prepreg by using a PN solution with a solid content of 30g and 32g T700 carbon fiber unidirectional cloth, and introducing an inorganic particle toughening agent into an interlayer region when the prepreg still has certain spreadability: boron carbide (B) having a particle size of 5 μm4C) The addition amount of the toughening agent is introduced according to the mass ratio of the solid content of the resin to the toughening agent of 90: 10.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedures are 200 ℃/0.5h, 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. After the post-curing is finished, the composite material is taken out after the post-curing is cooled to room temperature along with the furnace, and 10 wt% B is obtained4C modified high-strength high-toughness phthalonitrile-based composite material.
Cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 3.
TABLE 310 wt% B4C modified high-strength high-toughness phthalonitrile-based composite material
Example 4
After bisphenol A type phthalonitrile resin monomer and amino phthalonitrile curing agent powder are mixed according to the mass ratio of 95:5, the resin powder and acetone are heated and blended at the temperature of 70 ℃ according to the mass ratio of 1:4, and the powder is dissolved in the acetone to form clear and uniform PN solution.
Preparing a wet prepreg by using a PN solution with a solid content of 30g and 32g T700 carbon fiber unidirectional cloth, and introducing a thermoplastic resin particle toughening agent into an interlayer region when the prepreg still has certain spreadability: thermoplastic Polyimide (PI) particles with the particle size of 10 mu m, wherein the addition amount of the toughening agent is introduced according to the mass ratio of the solid content of the resin to the toughening agent of 95: 5.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedures are 200 ℃/0.5h, 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. And after post-curing is finished, cooling the composite material to room temperature along with the furnace, and taking out the composite material to obtain the PI modified high-strength high-toughness phthalonitrile-based composite material with the weight percent of 5%.
Cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 4.
Performance of 45% wt PI modified high-strength high-toughness phthalonitrile-based composite material in table
Example 5
After bisphenol A type phthalonitrile resin monomer and amino phthalonitrile curing agent powder are mixed according to the mass ratio of 95:5, the resin powder and acetone are heated and blended at the temperature of 70 ℃ according to the mass ratio of 1:4, and the powder is dissolved in the acetone to form clear and uniform PN solution.
Preparing a wet prepreg by using a PN solution with a solid content of 30g and 32g T700 carbon fiber unidirectional cloth, and introducing a thermoplastic resin particle toughening agent into an interlayer region when the prepreg still has certain spreadability: thermoplastic Polyimide (PI) particles with the particle size of 10 mu m, wherein the addition amount of the toughening agent is introduced according to the mass ratio of the solid content of the resin to the toughening agent of 85: 15.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedures are 200 ℃/0.5h, 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. And after post-curing is finished, cooling the composite material to room temperature along with the furnace, and taking out the composite material to obtain the 15 wt% PI modified high-strength high-toughness phthalonitrile-based composite material.
Cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 5.
Performance of PI modified high-strength high-toughness phthalonitrile-based composite material with weight percent of Table 515%
Example 6
After bisphenol A type phthalonitrile resin monomer and amino phthalonitrile curing agent powder are mixed according to the mass ratio of 95:5, the resin powder and acetone are heated and blended at the temperature of 70 ℃ according to the mass ratio of 1:4, and the powder is dissolved in the acetone to form clear and uniform PN solution.
Preparing a wet prepreg by using a PN solution with a solid content of 30g and 32g T700 carbon fiber unidirectional cloth, and introducing a thermoplastic resin particle toughening agent into an interlayer region when the prepreg still has certain spreadability: polyether-ether-ketone (PEEK) particles with the particle size of 30 mu m are introduced according to the mass ratio of the solid content of the resin to the toughening agent of 90: 10.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedures are 200 ℃/0.5h, 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. And after post-curing is finished, cooling the composite material to room temperature along with the furnace, and taking out the composite material to obtain the 10 wt% PEEK modified high-strength high-toughness phthalonitrile-based composite material.
Cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 6.
TABLE 610 wt% PEEK modified high-strength high-toughness phthalonitrile-based composite material performance
Example 7
After bisphenol A type phthalonitrile resin monomer and amino phthalonitrile curing agent powder are mixed according to the mass ratio of 95:5, the resin powder and acetone are heated and blended at the temperature of 70 ℃ according to the mass ratio of 1:4, and the powder is dissolved in the acetone to form clear and uniform PN solution.
Preparing a wet prepreg by using a PN solution with a solid content of 30g and 32g T700 carbon fiber unidirectional cloth, and introducing an inorganic particle toughening agent into an interlayer region when the prepreg still has certain spreadability: silicon carbide (SiC) particles with the particle size of 3 mu m, and the addition amount of the toughening agent is introduced according to the mass ratio of the solid content of the resin to the toughening agent of 90: 10.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedures are 200 ℃/0.5h, 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. And after post-curing is finished, cooling the composite material to room temperature along with the furnace, and taking out the composite material to obtain the 10 wt% SiC modified high-strength high-toughness phthalonitrile-based composite material.
Cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 7.
TABLE 710 wt% SiC modified high-strength high-toughness phthalonitrile-based composite material
Comparative example 1
Mixing a bisphenol A type phthalonitrile resin monomer and an amino phthalonitrile curing agent powder according to a mass ratio of 95:5, heating and blending the resin powder and acetone at a mass ratio of 1:4 at 70 ℃ to dissolve the powder in the acetone to form a clear and uniform PN solution, preparing the PN solution with a solid content of 30g and 32g T700 carbon fiber unidirectional fabric into a wet prepreg, and then carrying out toughening treatment.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedures are 200 ℃/0.5h, 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. And after post-curing is finished, cooling the composite material to room temperature along with the furnace, and taking out the composite material to obtain the unmodified phthalonitrile-based composite material.
Cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 8.
TABLE 8 Properties of unmodified phthalonitrile based composites
Comparative example 2
After bisphenol A type phthalonitrile resin monomer and amino phthalonitrile curing agent powder are mixed according to the mass ratio of 95:5, thermoplastic Polyimide (PI) particles with the particle size of 10 mu m are mixed with the solid resin content and the toughening agent according to the mass ratio of 90:10, and the mixture is melted and mixed at 100 ℃ to prepare the dry prepreg.
Cutting the prepreg into proper size after removing the solvent according to the proportion of 0]8The layers are sequentially paved to obtain a prefabricated body, the prefabricated body is placed in a steel mould, the steel mould is heated to 200 ℃ on a hot press, the pressure of 5MPa is gradually applied, and the precuring procedure is 200 ℃/0.5h and 250 ℃/2h and 280 ℃/2 h. And (3) cooling the laminated board to room temperature along with the furnace, taking the laminated board out of the mold, trimming burrs, transferring the laminated board to a high-temperature blast drying oven, and performing post-curing according to the procedures of 315 ℃/4h and 375 ℃/2 h. And after post-curing is finished, cooling the composite material to room temperature along with the furnace, and taking out the composite material to obtain the blending modified phthalonitrile-based composite material.
Cutting a bending performance test sample according to GB/T3356-; the interlaminar shear strength test specimen is cut according to GB/T3357-1982, and the size is 20mm multiplied by 6mm multiplied by 2 mm; the above properties were tested on an Instron5567 universal mechanical tester. Dynamic mechanical analysis tests were carried out on a Netzsch 242c dynamic mechanical analyzer with sample sizes of 30mm x 8mm x 2mm and test spans of 10 mm. The test results are shown in table 9.
TABLE 9 Properties of blend-modified phthalonitrile-based composite materials
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A phthalonitrile-based composite material comprising a plurality of matrix layers in the form of a stack, each matrix layer comprising a fibre-reinforced phthalonitrile resin;
the composite material further comprises at least one interlayer region, each interlayer region is formed between two adjacent matrix layers, and each interlayer region contains toughening particles selected from thermoplastic resin particles and/or inorganic particles.
2. Composite material according to claim 1, characterized in that said thermoplastic resin particles are selected from thermoplastic particles having a glass transition temperature higher than 250 ℃, preferably at least one of thermoplastic polyimide, polyetheretherketone, polyaryletherketone, modified polyaryletherketone (PEK-C), polyetherimide, polybenzimidazole, polybenzoxazole, polyethersulfone;
preferably, the inorganic particles are selected from inorganic particles having high heat resistance, such as at least one of boron carbide, silicon carbide, boron nitride, and alumina.
Preferably, the toughening particles have an average particle size of no more than 30 μm.
3. The composite material according to claim 1 or 2, wherein the phthalonitrile resin is at least one selected from the group consisting of primary phthalonitrile resins (which are obtained by curing a small-molecule monomer containing a phthalonitrile group with a curing agent), secondary phthalonitrile resins (which contain a molecular segment terminated with a phthalonitrile group), and other resins having a phthalonitrile group and having it as a crosslinking site.
4. The composite material according to claim 3, wherein the small molecule monomer comprising a phthalonitrile group has a structure according to formula (1):
wherein R is selected from the following structures:
preferably, R is selected from the following structures:
preferably, the curing agent is selected from substances having a phthalonitrile group containing an amino group and/or a hydroxyl group; preferably a substance having a phthalonitrile group containing an amino group; preferably, the amino group-containing substance having a phthalonitrile group has the structure shown in formula (2):
preferably, the primary phthalonitrile resin is selected from at least one of the compounds represented by the formula (a) and the formula (b):
5. composite material according to any of claims 1 to 4, characterized in that the reinforcing fibres are continuous fibres, preferably single or hybrid fabrics selected from carbon fibres, glass fibres, quartz fibres, aramid fibres; preferably, the fabric is a unidirectional fabric or a two-dimensional fabric;
preferably, the interlayer region has a sea-island structure including the phthalonitrile resin and the toughening particles therein;
preferably, the toughening particles account for 5-60% of the mass of the phthalonitrile resin;
preferably, the glass transition temperature of the composite material is higher than 420 ℃;
preferably, the flexural strength of the composite material is higher than 1400 MPa;
preferably, the flexural modulus of the composite material is greater than 90 GPa;
preferably, the interlaminar shear strength of the composite is not less than 50 MPa.
6. The process for the preparation of a phthalonitrile based composite material according to any of claims 1 to 5, characterized in that it comprises the following steps:
(1) preparing a resin prepreg containing phthalonitrile resin and reinforcing fibers;
(2) attaching toughening particles to the surface of the resin prepreg to obtain a toughened phthalonitrile resin prepreg;
(3) and (3) paving the toughened phthalonitrile resin prepreg in the step (2) to obtain a prefabricated body, and curing the prefabricated body to obtain the phthalonitrile-based composite material.
7. The production method according to claim 6, wherein in the step (1), the phthalonitrile resin is produced from a phthalonitrile resin monomer and a curing agent;
preferably, the mass ratio of the phthalonitrile resin to the reinforcing fibers is 1 (1-1.5);
preferably, the resin prepreg is prepared by a solvent method or a melt method, and preferably by a solvent method.
8. The production method according to claim 6 or 7, wherein in the step (3), the curing includes pre-curing and post-curing;
preferably, the prefabricated body is placed in a vacuum bag or a steel mould for precuring, and then is transferred to an oven for post-curing;
preferably, the pre-curing is a hot pressing process.
9. A phthalonitrile based composite material prepared by the process according to any one of claims 6 to 8.
10. Use of the phthalonitrile based composite material according to any of claims 1-5, 9 in aerospace high temperature resistant materials.
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