CN116396613A - Polyimide resin matrix composite material and preparation method thereof - Google Patents
Polyimide resin matrix composite material and preparation method thereof Download PDFInfo
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- CN116396613A CN116396613A CN202310242534.4A CN202310242534A CN116396613A CN 116396613 A CN116396613 A CN 116396613A CN 202310242534 A CN202310242534 A CN 202310242534A CN 116396613 A CN116396613 A CN 116396613A
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- capping agent
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- dianhydride
- polyimide
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 38
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 239000009719 polyimide resin Substances 0.000 title abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000011159 matrix material Substances 0.000 title abstract description 5
- 239000004642 Polyimide Substances 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000835 fiber Substances 0.000 claims abstract description 21
- 150000004985 diamines Chemical class 0.000 claims abstract description 9
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 239000004305 biphenyl Substances 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229920001169 thermoplastic Polymers 0.000 claims description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 8
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 7
- -1 diphenyl ether diamine Chemical class 0.000 claims description 7
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 6
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 6
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 claims description 4
- UPGRRPUXXWPEMV-UHFFFAOYSA-N 5-(2-phenylethynyl)-2-benzofuran-1,3-dione Chemical group C=1C=C2C(=O)OC(=O)C2=CC=1C#CC1=CC=CC=C1 UPGRRPUXXWPEMV-UHFFFAOYSA-N 0.000 claims description 4
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 claims description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000012783 reinforcing fiber Substances 0.000 claims description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 claims description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- GFUCMNMXYOVTDJ-UHFFFAOYSA-N 2,4-diamino-6-butan-2-ylphenol Chemical compound CCC(C)C1=CC(N)=CC(N)=C1O GFUCMNMXYOVTDJ-UHFFFAOYSA-N 0.000 claims description 2
- MILSYCKGLDDVLM-UHFFFAOYSA-N 2-phenylpropan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)C1=CC=CC=C1 MILSYCKGLDDVLM-UHFFFAOYSA-N 0.000 claims description 2
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 claims description 2
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 claims description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 claims description 2
- BBTGUNMUUYNPLH-UHFFFAOYSA-N 5-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 BBTGUNMUUYNPLH-UHFFFAOYSA-N 0.000 claims description 2
- 102100035915 D site-binding protein Human genes 0.000 claims description 2
- 101000873522 Homo sapiens D site-binding protein Proteins 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229920006259 thermoplastic polyimide Polymers 0.000 abstract description 10
- 238000004132 cross linking Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 2
- 239000004952 Polyamide Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract 2
- 229920002647 polyamide Polymers 0.000 abstract 2
- 235000010290 biphenyl Nutrition 0.000 abstract 1
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000012216 screening Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 28
- 239000011347 resin Substances 0.000 description 23
- 229920005989 resin Polymers 0.000 description 23
- 238000005452 bending Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000805 composite resin Substances 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012815 thermoplastic material Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004963 Torlon Substances 0.000 description 1
- 229920003997 Torlon® Polymers 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000002466 imines Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification 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
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/046—Reinforcing macromolecular compounds with loose or coherent fibrous material with synthetic macromolecular fibrous material
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
Abstract
The invention relates to a polyimide resin matrix composite material and a preparation method thereof. The method comprises the following specific steps: the structural monomers of biphenyl dianhydride and diamine monomer with high thermochemical stability are screened based on the group density, the main chain structure with melting and crystallization characteristics is optimized, and the polyamide acid molecular chain structure is prepared in a polar solvent; the preparation method comprises the steps of respectively screening an inert end-capping agent for controlling molecular chain growth and an active end-capping agent with a bulk crosslinking characteristic, adding the inert end-capping agent and the active end-capping agent into a polyamide acid solution according to a certain proportion, reacting to obtain a homogeneous phase molten polyimide oligomer, and impregnating the homogeneous phase molten polyimide oligomer into fiber holes, fiber surfaces and fiber braid gaps under the action of a pressure field to form the heat-resistant high-strength thermoplastic polyimide composite material. The method has controllable process and excellent process, and can realize industrial mass production; the product has excellent thermal and mechanical properties.
Description
Technical Field
The invention relates to a polyimide-based composite material and a preparation method thereof, in particular to a polyimide resin-based fiber reinforced composite material with controllable crosslinking degree and a preparation method thereof.
Background
Polyimide (PI) is a polymer which is formed by taking five-membered imide as a main chain, and is obtained by copolymerization and cyclization dehydration of diamine and dianhydride, the raw materials have different diamine and dianhydride structures, and the PI resin has different performances. Aromatic PI was first prepared in the university of california in the united states in 1908, but the structure and properties of the polymer were not fully known at the time and therefore have not received attention. In 1961, dupont synthesized a poly-pyromellitic imide film (Kapton) by a two-step process using a condensation reaction of aromatic diamine and dianhydride, and PI resins formally entered the commercial application field.
PI materials have evolved rapidly over the last few decades, with representative products including Kapton and Vespel from dupont, torlon from Amoco, ultem from GE, and Aurum from mitsunobu chemical, among others. Along with the improvement of material performance, the application field of the material is also expanded from films to various fields such as coating, composite materials, fibers, photoresist and the like. From the viewpoint of the processing method, PI can be classified into thermosetting polyimide (TSPI) and Thermoplastic Polyimide (TPI). TSPI has excellent heat resistance and high strength, but generally has poor processability due to inability to melt process. The TPI has excellent comprehensive performance, is suitable for injection molding and extrusion, and can be subjected to secondary hot melt processing based on particle materials or film materials, and the processability is excellent. Thus, recent decades have seen a trend from TSPI to TPI. In recent years, it has been found that TPI can plasticize at higher pressures, affecting composite properties. By adding an initiator and other means to activate active groups in the TPI chain under specific conditions, crosslinkable free radicals are generated, so that the controllable crosslinking of the TPI is realized, and the resin has the advantages of TSPI (high temperature resistance and high stability) and TPI (easy molding and processing) and becomes a research hot spot.
The PI resin-based composite material is one of the resin-based composite materials for the structure with the highest temperature resistance level at present, and has been widely used in the fields of aerospace, space technology and the like abroad. For example, the high temperature carbon fiber reinforced PMR15 series high temperature resistant resins developed by NASA are widely used in aerospace engines, missiles, reusable vehicles (RLV) and the like, and have a long-term use temperature of about 300 ℃. Composite molding techniques depend on production condition constraints, product size, use requirements, and material processing engineering. The method is characterized in that a proper composite material forming method is selected according to the characteristics of the components and the performances of the PI resin-based composite material, a composite material forming process model is established, the accurate regulation and control of the resin infiltration process and the curing forming are realized, and the multifunctional composite material is prepared according to the characteristics of the functional resin material, so that the method becomes a hot spot of current research.
The aromatic diamine and dianhydride have high melting point and activity, and the polymerization and imidization reaction in the polyimide preparation process is reversible reaction, so that various variant compounds and polymers can be generated, and the removal of water as a low-boiling product can shift the equilibrium level to generate stable high-polymerization-state imine ring structure-polyimide. The solid monomer is dissolved in aprotic polar solvents such as N, N' -dimethylacetamide (DMAc) and the like, the polymerization degree and molecular weight distribution of the polyamic acid can be regulated, and the target polymer is obtained after chemical or thermal imidization and solvent removal. However, the solution polymerization process is complicated, and impurities, decomposition, association residues and the like of the organic solvent affect the structure and performance of polyimide to different degrees, while the performance advantage of polyimide resin is not fully reflected when the fiber prepreg is prepared by a wet method, and some occasions are inferior to epoxy resin, phenolic resin and the like. The design and preparation of the novel chemical structure of the controllable thermal crosslinking thermoplastic polyimide and the composite material provide technical support for widening the application of the PI-based composite material in the emerging high-end fields of aerospace, military and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a polyimide resin matrix composite material, and the other aim of the invention is to provide a preparation method of the polyimide resin matrix composite material.
The technical scheme of the invention is that the polyimide-based composite material is characterized in that the components in the fiber-reinforced polyimide-based composite material and the percentage content of the components in the total mass of the composite material are as follows:
polyimide: 20 to 95 percent of
Reinforcing fibers: 5% -80%.
Preferably, the reinforcing fiber is carbon fiber, high silica fiber, aramid fiber, quartz fiber or a braided fabric of the above fibers.
The invention also provides a method for preparing the polyimide-based composite material, which comprises the following specific steps:
placing flexible diamine and dianhydride monomer in a polar solvent according to a molar ratio of 1 (1-1.1) to react into homogeneous phase under stirring, adding an inert end-capping agent and an active end-capping agent successively, and reacting under stirring to obtain thermoplastic PAA oligomer with mass concentration of 10% -40%;
and (3) placing the reinforced fiber in the thermoplastic PAA oligomer prepared in the step (1) for pre-impregnation, placing the preform in a mold, and respectively performing hot molding process forming and cold pressing demolding treatment to obtain the polyimide-based composite material.
Preferably, the diamine in step (1) is one or two of dimethyl diphenyl methane diamine (DMMDA), 1, 3-bis (3-aminophenoxy) benzene (BAPB), 4' -bisphenol A diphenyl ether diamine (BAPP), 4' -bis (4-aminophenoxy) diphenyl sulfone (BAPS), 4' -bis (4-aminophenoxy) diphenyl ether (BAPE), diaminodiphenyl (methyl) ketone (DABP), 4' -Diaminotriphenylamine (DATPA), 4' -diaminodiphenyl Methane (MDA) or diaminodiphenyl sulfone (DDS); the dianhydride is one or two of pyromellitic dianhydride (PMDA), 3, 4-diphenyl tetracarboxylic dianhydride (BPDA), 4' -oxydiphthalic anhydride (ODPA), heterogeneous diphenyl sulfide dianhydride (TDPA), triphenyl diether tetracarboxylic dianhydride (HQDPA), benzophenone Tetracarboxylic Dianhydride (BTDA), benzophenone tetracarboxylic dianhydride (BDTA), bisphenol A dianhydride (BPADA), monoether tetracarboxylic dianhydride or 3,3', 4' -diphenyl sulfone tetracarboxylic anhydride (DSDA); the inert end capping agent is phthalic anhydride or 1,2,3, 6-tetrahydrophthalic anhydride; the active end-capping agent is 4-phenylethynyl phthalic anhydride (4-PEPA) or phenylacetylene trimethyl anhydride (PETA); the polar solvent is N, N '-dimethylacetamide (DMAc), N' -Dimethylformamide (DMF) or N-methylpyrrolidone (NMP).
Preferably, a certain temperature in the step (1) is controlled to be 10-40 ℃; adding diamine and dianhydride, and stirring for reaction for 1-2h; after the end capping agent is added, the reaction time is 2-7h.
Preferably, the molar ratio of the inert end-capping agent, the reactive end-capping agent and the dianhydride is 0.5-2.5:1.
Preferably, the pre-impregnation time in the step (2) is 10-30min; the temperature of the hot molding is 320-400 ℃, the pressure condition is 5-30Mpa, and the molding time is 20-90min; the pressure condition of cold press demoulding is 10-40MPa, and the pressure maintaining time is 5-30min.
The invention has controllable experimental operation process and mild implementation condition, and can realize mass production. Provides a simple and feasible method for preparing the polyimide-based composite material with controllable crosslinking degree and high performance. The material prepared by the method has excellent processability, high toughness, high strength and remarkably improved high temperature resistance.
The beneficial effects are that:
1. the composite material prepared by the method can design and regulate the crosslinking degree of the polymer molecular chain according to requirements.
2. The polymer material prepared in the invention is completely imidized resin during compounding with fiber, no volatile micromolecule is generated, the high-temperature high-melting rheological process window is widened, the end group crosslinking solidification is realized, and the high-temperature resistance characteristic of the composite material is obviously improved.
3. Polyimide resins combine the processability of thermoplastic materials with the high strength and toughness of thermoset materials. The material has higher decomposition residual rate in N2 environment and shows more ideal heat stability.
Drawings
FIG. 1 shows DSC data (STPN 1.0-2.5) of the composites of examples 2-5; wherein STPN is the number of the composite material, and 1.0-2.5 represents that the molar ratio of the added inert end capping agent to the active end capping agent to the dianhydride is 1-2.5:1 respectively.
Detailed Description
Example 1
1.3056g of DDS is added into 7g of DMF solvent at 25 ℃, 1.6842g of BDTA with the same molar quantity as the DDS is added in batches after stirring and dissolving, the mixture is stirred for 2 hours to form a homogeneous phase, 0.5662g of phthalic anhydride serving as an inert end-capping agent and 0.5:1 of dianhydride molar ratio are added successively, and stirring is continued for 5 hours to prepare the thermoplastic PAA oligomer with the mass concentration of 30%.
3g of carbon fiber cloth is immersed in PAA for 30min, the two mixtures are placed in a die, hot-pressed for 50min at 320 ℃ and 20MPa, taken out, kept in a cold press for 5min at 10MPa, and demoulded, wherein the mass ratio of resin to fiber in the prepared composite material is 50:50.
The bending strength of the sample in the embodiment is 760MPa, the bending modulus is 52500MPa, and the sample has better high-strength and high-toughness characteristics. The glass transition temperature of the resin material is 268.6 ℃, and the resin material also shows better processability. The resin material has a decomposition residual rate of 56.42% in N2 atmosphere at 800 ℃ and shows good heat resistance.
Example 2
At 20 ℃, 0.7618g of MDA is added into 20g of DMF solvent, 1.2488g of dianhydride BTDA with the molar ratio of 1.1:1 is added in batches after stirring and dissolving, the mixture is stirred for 1.5 hours to form a homogeneous phase, 0.5934g of inert end-capping agent tetrahydrophthalic anhydride and 1.0773g of active end-capping agent are added successively, and stirring is continued for 4 hours, so that the thermoplastic PAA oligomer with the mass concentration of 10% is prepared.
0.1064g of carbon fiber is immersed in PAA for 20min, the two mixtures are placed in a die, hot-pressed for 40min at 330 ℃ and 10Mpa, taken out, kept at 20MPa for 20min in a cold press, and demoulded, wherein the mass ratio of resin to fiber in the prepared composite material is 95:5.
The sample in the embodiment has the bending strength of 560MPa and the bending modulus of 43000MPa, and shows better high-strength and high-toughness characteristics. The glass transition temperature of the resin material was 268 ℃ (see fig. 1), which also showed good processability. The resin material has a decomposition residual rate of 50.47% in an N2 atmosphere at 800 ℃ and shows good heat resistance.
Example 3
At 15 ℃, adding 1.431g of BAPP into 14.7g of NMP solvent, stirring and dissolving, adding 1.1354g of ODPA with the mol ratio of BAPP being 1.05:1 in batches, stirring for 1h to form a homogeneous phase, adding 0.8132g of phthalic anhydride serving as an inert end-capping agent and 0.8132g of PETA1.5166g of PETA1 serving as an active end-capping agent with the mol ratio of 1.5:1 in sequence, and continuously stirring for 7h to prepare the thermoplastic PAA oligomer with the mass concentration of 25%.
Soaking 19.6g of high silica fiber in PAA for 10min, placing the two mixtures in a die, hot-pressing for 90min at 400 ℃ and 30MPa, taking out, maintaining the pressure in a cold press for 30min at 40MPa, and demolding, wherein the mass ratio of resin to fiber in the prepared composite material is 20:80.
The bending strength of the sample in the embodiment is 450MPa, the bending modulus is 41500MPa, and the sample has better high-strength and high-toughness characteristics. The glass transition temperature of the resin material was 267.2 ℃ (see fig. 1), and also showed good workability. The resin material has a decomposition residual rate of 52.18% in an N2 atmosphere at 800 ℃ and shows good heat resistance.
Example 4
1.8421g of mBAPB is added into 27.6g of NMP solvent at 10 ℃, 1.0906g of PMDA with the same molar quantity as mBAPB is added in batches after stirring and dissolving, the mixture is stirred for 1h to form a homogeneous phase, 1.4812g of phthalic anhydride serving as an inert end-capping agent and 1.4812g of 4-PEPA2.4823g of an active end-capping agent with the molar ratio of 2:1 are added successively, and stirring is continued for 2h, so that the thermoplastic PAA oligomer with the mass concentration of 20% is prepared.
4.62g of aramid fiber is immersed in PAA for 10min, the two mixtures are placed in a die, hot-pressed for 20min at 350 ℃ and 10MPa, taken out, kept at 30MPa for 10min in a cold press, and demoulded, wherein the mass ratio of resin to fiber in the prepared composite material is 60:40.
The bending strength of the sample in the embodiment is 530MPa, the bending modulus is 45500MPa, and the better high-strength high-toughness characteristic is shown. The glass transition temperature of the resin material was 264.9 ℃ (see fig. 1), and also showed good workability. The resin material has a decomposition residual rate of 53.65% in an N2 atmosphere at 800 ℃ and shows good heat resistance.
Example 5
1.9222g of BAPE is added into 13.3g of DMAc solvent at 40 ℃, 1.0906g of PMDA with the same molar quantity as the BAPE is added in batches after stirring and dissolving, the mixture is stirred for 1.5 hours to form a homogeneous phase, 1.9019g of tetrahydrophthalic anhydride serving as an inert end-capping agent and 4-PEPA3.1029g of active end-capping agent with the molar ratio of 2.5:1 are added successively, and stirring is continued for 3 hours to prepare the thermoplastic PAA oligomer with the mass concentration of 40%.
3.79g of quartz fiber is immersed in PAA for 15min, the two mixtures are placed in a mould, hot-pressed for 30min at 380 ℃ and 5MPa, taken out, kept in a cold press for 15min under 15MPa, and demoulded, wherein the mass ratio of resin to fiber in the prepared composite material is 70:30.
The bending strength of the sample in the embodiment is 625MPa, and the bending modulus is 48000MPa, so that the sample has better high-strength and high-toughness characteristics. The glass transition temperature of the resin material was 266.7 ℃ (see fig. 1), and also showed good workability. The resin material has a decomposition residual rate of 51.04% in an N2 atmosphere at 800 ℃ and shows good heat resistance.
The polyimide resins of examples 2 to 5 described above combine the processability of thermoplastic materials with the high strength and high toughness of thermosetting materials. The mechanical properties of the materials are shown in the following table:
the material has higher decomposition residual rate in N2 environment and shows more ideal heat stability. The thermal decomposition parameters are shown in the following table:
Claims (7)
1. the polyimide-based composite material is characterized in that the components in the fiber-reinforced polyimide-based composite material and the percentage content of the components in the total mass of the composite material are as follows:
polyimide: 20 to 95 percent of
Reinforcing fibers: 5% -80%.
2. The polyimide-based composite material according to claim 1, wherein the reinforcing fiber is carbon fiber, high silica fiber, aramid fiber, quartz fiber or a braid of the above fibers.
3. A method of preparing the polyimide-based composite material of claim 1, comprising the specific steps of:
(1) Placing flexible diamine and dianhydride monomer in a polar solvent according to a molar ratio of 1 (1-1.1) to react into homogeneous phase under stirring, adding an inert end-capping agent and an active end-capping agent successively, and reacting under stirring to obtain thermoplastic PAA oligomer with mass concentration of 10% -40%;
(2) And (3) placing the reinforced fiber in the thermoplastic PAA oligomer prepared in the step (1) for pre-impregnation, placing the preform in a mold, and respectively performing hot molding process forming and cold pressing demolding treatment to obtain the polyimide-based composite material.
4. A method according to claim 3, characterized in that the diamine in step (1) is one or two of dimethyl diphenyl methane diamine (DMMDA), 1, 3-bis (3-aminophenoxy) benzene (BAPB), 4' -bisphenol a diphenyl ether diamine (BAPP), 4' -bis (4-aminophenoxy) diphenyl sulfone (BAPS), 4' -bis (4-aminophenoxy) diphenyl ether (BAPE), diaminodiphenyl (methyl) ketone (DABP), 4' -Diaminotriphenylamine (DATPA), 4' -diaminodiphenyl Methane (MDA) or diaminodiphenyl sulfone (DDS); the dianhydride is one or two of pyromellitic dianhydride (PMDA), 3, 4-diphenyl tetracarboxylic dianhydride (BPDA), 4' -oxydiphthalic anhydride (ODPA), heterogeneous diphenyl sulfide dianhydride (TDPA), triphenyl diether tetracarboxylic dianhydride (HQDPA), benzophenone Tetracarboxylic Dianhydride (BTDA), benzophenone tetracarboxylic dianhydride (BDTA), bisphenol A dianhydride (BPADA), monoether tetracarboxylic dianhydride or 3,3', 4' -diphenyl sulfone tetracarboxylic anhydride (DSDA); the inert end capping agent is phthalic anhydride or 1,2,3, 6-tetrahydrophthalic anhydride; the active end-capping agent is 4-phenylethynyl phthalic anhydride (4-PEPA) or phenylacetylene trimethyl anhydride (PETA); the polar solvent is N, N '-dimethylacetamide (DMAc), N' -Dimethylformamide (DMF) or N-methylpyrrolidone (NMP).
5. A method according to claim 3, characterized in that the temperature in step (1) is controlled to be 10 ℃ to 40 ℃; adding diamine and dianhydride, and stirring for reaction for 1-2h; after the end capping agent is added, the reaction time is 2-7h.
6. The process of claim 3 wherein the molar ratio of inert capping agent, reactive capping agent to dianhydride is from 0.5 to 2.5:1.
7. A method according to claim 3, wherein the pre-impregnation time in step (2) is from 10 to 30 minutes; the temperature of the hot molding is 320-400 ℃, the pressure condition is 5-30Mpa, and the molding time is 20-90min; the pressure condition of cold press demoulding is 10-40MPa, and the pressure maintaining time is 5-30min.
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