CN116426123A - Bismaleimide resin composition, composite material and preparation method thereof - Google Patents
Bismaleimide resin composition, composite material and preparation method thereof Download PDFInfo
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- CN116426123A CN116426123A CN202310701355.2A CN202310701355A CN116426123A CN 116426123 A CN116426123 A CN 116426123A CN 202310701355 A CN202310701355 A CN 202310701355A CN 116426123 A CN116426123 A CN 116426123A
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- 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 title claims abstract description 148
- 229920003192 poly(bis maleimide) Polymers 0.000 title claims abstract description 140
- 239000011342 resin composition Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 131
- 239000011347 resin Substances 0.000 claims abstract description 131
- 239000003822 epoxy resin Substances 0.000 claims abstract description 51
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 51
- 239000001301 oxygen Substances 0.000 claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 34
- QIRNGVVZBINFMX-UHFFFAOYSA-N 2-allylphenol Chemical compound OC1=CC=CC=C1CC=C QIRNGVVZBINFMX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 28
- TYGPTXIVDGYHPB-UHFFFAOYSA-N 2,3-bis(prop-2-enyl)phenol Chemical compound OC1=CC=CC(CC=C)=C1CC=C TYGPTXIVDGYHPB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 229920001451 polypropylene glycol Polymers 0.000 claims description 39
- 238000001723 curing Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 22
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 20
- 229920000570 polyether Polymers 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 11
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000011415 microwave curing Methods 0.000 claims description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000010030 laminating Methods 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 4
- -1 allyl compound Chemical class 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- 229920000049 Carbon (fiber) Polymers 0.000 description 11
- 239000004917 carbon fiber Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000012986 modification Methods 0.000 description 10
- 230000004048 modification Effects 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000004593 Epoxy Chemical group 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000006384 oligomerization reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- LSEBTZWHCPGKEF-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C=C1 LSEBTZWHCPGKEF-UHFFFAOYSA-N 0.000 description 1
- DYDWKSVZHZNBLO-UHFFFAOYSA-N 4-prop-2-enoxybenzoic acid Chemical compound OC(=O)C1=CC=C(OCC=C)C=C1 DYDWKSVZHZNBLO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions 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 C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
-
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T50/00—Aeronautics or air transport
- Y02T50/40—Weight reduction
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a bismaleimide resin composition, a composite material and a preparation method thereof, wherein the bismaleimide resin composition comprises the following components in parts by weight: 100 parts of bismaleimide resin, 30-50 parts of allylphenol oxygen resin and 20-45 parts of diallyl bisphenol A; the preparation raw materials of the allylphenol oxygen resin comprise diallyl phenol, flexible side chain modified epoxy resin and a catalyst; diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the catalyst is 1:0.4-0.5:0.05-0.15. In the bismaleimide resin composition, the bismaleimide resin reacts with allylphenoxy resin and allyl in diallyl bisphenol A and active C=C on a bismaleimide resin ring to generate a high-crosslinking-degree ring-formed flexible resin, so that the toughness of the bismaleimide resin is improved, and a flexible chain segment is introduced into the bismaleimide resin through allylphenoxy resin, so that the toughness of the bismaleimide resin is further improved, and meanwhile, the impact resistance of the bismaleimide resin is improved.
Description
Technical Field
The invention belongs to the technical field of bismaleimide resin matrix composite materials, and particularly relates to a bismaleimide resin composition, a bismaleimide resin matrix composite material and a preparation method of the bismaleimide resin composition.
Background
The bismaleimide resin belongs to polyimide, and has the excellent characteristics of higher strength and modulus, good high temperature resistance, radiation resistance, damp and heat resistance, low moisture absorption rate, small thermal expansion coefficient and the like. Meanwhile, the bismaleimide resin also has fluidity and stamping property similar to those of epoxy resin, and has good manufacturability, so that the bismaleimide resin has good application prospect in the fields of aerospace and the like. However, the distance between the chains of the difunctional groups of the bismaleimide resin monomer is short, and the crosslinking density is high, so that the defects of poor toughness, brittle quality and the like of the cured product exist, the impact resistance and the stress cracking resistance of the cured product are poor, and the application of the cured product is limited.
Therefore, the bismaleimide resin needs to be modified to improve its toughness. At present, the method for toughening and modifying the bismaleimide resin mainly comprises the following steps: allyl compound modification, diamine chain extension modification, thermoplastic resin modification, thermosetting resin modification, inorganic functional material modification and the like. The modification of the allyl compound is a main modification means, wherein allyl in the allyl compound is utilized to carry out diene addition with active C=C on a bismaleimide ring, then the C=C on the maleimide ring and an intermediate product are subjected to Diels-Alder and anion imide oligomerization reaction to generate the tough resin with a high crosslinking degree and a ring structure, so that the toughness of the bismaleimide resin is improved. For example, chinese patent publication No. CN 112679357A discloses a modified allyl compound having a cyclopentadiene structure and containing a benzene ring or a benzene ring substituted with a linear alkane having a relatively low polarity, a modified bismaleimide prepolymer having a specific structure, which can improve the solubility of bismaleimide and reduce the crosslink density thereof, thereby reducing the water absorption, dielectric constant and dielectric loss value of resin and improving the heat resistance of resin, and its use. Chinese patent publication No. CN 104974346B discloses a method for preparing a liquid crystalline allyl compound modified bismaleimide resin, which includes 1, 4-bis (4-allyloxybenzoic acid) phenyl ester liquid crystalline allyl compound, 2' -diallyl bisphenol a and bismaleimide monomer. The modified bismaleimide resin can be dissolved in conventional low-boiling solvents such as acetone, chloroform and the like, has good curing and molding manufacturability, and a cured product of the modified bismaleimide resin has excellent heat resistance and toughness.
However, the current allyl compound modification method has limited toughening effect on the bismaleimide resin, the toughness of the bismaleimide resin still needs to be further improved, and the modified bismaleimide resin has a certain influence on the impact resistance and the heat resistance.
Disclosure of Invention
The invention provides a bismaleimide resin composition, a composite material and a preparation method thereof, which are used for solving the technical problems that the toughening effect of the existing modified bismaleimide resin is limited and the impact resistance and heat resistance of the modified bismaleimide resin are reduced.
In order to solve the above problems, a first aspect of the present invention provides a bismaleimide resin composition comprising the following components in parts by mass:
100 parts of bismaleimide resin, 30-50 parts of allylphenol oxygen resin and 20-45 parts of diallyl bisphenol A;
the preparation raw materials of the allylphenol oxygen resin comprise diallyl phenol, flexible side chain modified epoxy resin and a first catalyst; diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the first catalyst is 1:0.4-0.5:0.05-0.15.
Preferably, the bismaleimide resin composition comprises the following components in parts by weight:
100 parts of bismaleimide resin, 38-42 parts of allylphenol oxygen resin and 30-38 parts of diallyl bisphenol A;
in the preparation raw materials of the allylphenol oxygen resin, diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the first catalyst is 1:0.43-0.48:0.08-0.1.
Preferably, the preparation raw materials of the flexible side chain modified epoxy resin comprise epoxy resin, isocyanate-terminated polyether and a second catalyst, wherein the ratio of the raw materials is 1:6-7:0.005-0.01.
Preferably, the isocyanate-terminated polyether is prepared from toluene-2, 4-diisocyanate and polypropylene glycol; the dosage of toluene-2, 4-diisocyanate and polypropylene glycol satisfies that the molar ratio of-NCO in toluene-2, 4-diisocyanate to-OH in polypropylene glycol is 2:1.
Preferably, the polypropylene glycol is polypropylene glycol 4000.
Preferably, the diallyl phenol is diallyl bisphenol a; the epoxy resin is bisphenol A type epoxy resin; the first catalyst is quaternary ammonium salt; the second catalyst is dibutyl tin dilaurate.
The second aspect of the present invention provides a method for preparing the above bismaleimide resin composition, comprising the steps of:
melting allylphenol oxygen resin, adding bismaleimide resin, prepolymerizing for 10-30min at 130-140 ℃, adding diallyl bisphenol A, and continuing to react for 10-30min at 130-140 ℃ to obtain the bismaleimide resin composition.
A third aspect of the present invention provides a fiber-reinforced bismaleimide resin-based composite comprising a fiber-reinforced material and the above-described bismaleimide resin composition.
The fourth aspect of the present invention provides a method for preparing the fiber reinforced bismaleimide resin matrix composite, comprising the following steps:
and (3) impregnating the bismaleimide resin composition with a fiber reinforced material to obtain a prepreg, and then paving and laminating the prepreg, and then curing and forming by microwave to obtain the fiber reinforced bismaleimide resin matrix composite material.
Preferably, the microwave curing and forming adopts gradient heating and curing, and the gradient heating program is as follows: curing at 130-140 deg.C for 0.5-2 hr, then heating to 150-160 deg.C for 10-14 hr, and heating to 180-190 deg.C for 10-14 hr.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the bismaleimide resin composition, allylphenol-oxygen resin and diallyl bisphenol A are adopted to jointly modify bismaleimide resin, allylphenol-oxygen resin, allyl in diallyl bisphenol A and active C=C on a bismaleimide resin ring are subjected to diene addition, and then C=C on the maleimide ring and an intermediate product are subjected to Diels-Alder and anion imide oligomerization reaction to generate a tough resin with a high crosslinking degree and a ring structure, so that the toughness of the bismaleimide resin is improved;
2. the bismaleimide resin composition is prepared by ring-opening and polyaddition of phenolic hydroxyl groups on diallyl phenol and epoxy bonds in flexible side chain modified epoxy resin under the action of a catalyst, and after the reaction with the bismaleimide resin, introducing a flexible chain segment into the bismaleimide resin, so that the rigidity of a molecular chain is reduced, the highly symmetrical structure of the original bismaleimide resin is destroyed, the shock resistance of a cured product of the bismaleimide resin composition is improved, and the density of aromatic rings can be reduced by introducing the flexible chain segment, so that the aim of further toughening is fulfilled;
3. because the prepolymer viscosity of the allylphenol oxygen resin and the bismaleimide resin is larger, the process operability is poorer, and therefore, the bismaleimide resin composition can reduce the system viscosity and improve the process operability by adding the diallyl bisphenol A with low viscosity.
Drawings
FIG. 1 is a photograph showing the preparation of a bismaleimide resin composition in example 1 of the present invention;
FIG. 2 is a photograph showing the preparation of the bismaleimide resin composition of example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
At present, the main toughening modification method of the bismaleimide resin is allyl compound modification, however, the existing allyl compound modification method has limited toughening effect on the bismaleimide resin, the toughness of the bismaleimide resin still needs to be further improved, and the modified bismaleimide resin has a certain influence on the impact resistance and heat resistance of the bismaleimide resin.
To this end, a first aspect of the embodiment of the present invention provides a bismaleimide resin composition, comprising the following components in parts by mass:
100 parts of bismaleimide resin, 30-50 parts of allylphenol oxygen resin and 20-45 parts of diallyl bisphenol A;
the preparation raw materials of the allylphenol oxygen resin comprise diallyl phenol, flexible side chain modified epoxy resin and a first catalyst; diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the first catalyst is 1:0.4-0.5:0.05-0.15.
According to the bismaleimide resin composition provided by the embodiment of the invention, allylphenol-oxygen resin and diallyl bisphenol A are adopted to jointly modify bismaleimide resin, allylphenol-oxygen resin and allyl in diallyl bisphenol A are subjected to diene addition with active C=C on a bismaleimide resin ring, then the C=C on the maleimide ring is subjected to Diels-Alder and anionic imide oligomerization reaction with an intermediate product to generate a tough resin with a high crosslinking degree and a ring structure, so that the toughness of the bismaleimide resin is improved; the allylphenol oxygen resin is obtained by ring-opening polyaddition of phenolic hydroxyl groups on diallyl phenol and epoxy bonds in flexible side chain modified epoxy resin under the action of a catalyst, and after the allylphenol oxygen resin reacts with bismaleimide resin, a flexible chain segment is introduced into the bismaleimide resin, so that the rigidity of a molecular chain is reduced, the highly symmetrical structure of the original bismaleimide resin is destroyed, the shock resistance of a cured product of the bismaleimide resin is improved, and the density of aromatic rings can be reduced by introducing the flexible chain segment, so that the purpose of further toughening is achieved. In addition, because the prepolymer of the allylphenoxy resin and the bismaleimide resin has higher viscosity, the process operability is poor, and therefore, the system viscosity can be reduced and the process operability is improved by adding the diallyl bisphenol A with low viscosity.
In some embodiments, the bismaleimide resin composition includes the following components in parts by mass:
100 parts of bismaleimide resin, 38-42 parts of allylphenol oxygen resin and 30-38 parts of diallyl bisphenol A;
in the preparation raw materials of the allylphenol oxygen resin, diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the first catalyst is 1:0.43-0.48:0.08-0.1.
The bismaleimide resin composition further optimizes the mass parts of the allylphenol oxygen resin and the diallyl bisphenol A in the bismaleimide resin composition, and the excessive or insufficient allylphenol oxygen resin and diallyl bisphenol A in the composition can have obvious influence on the toughness, the impact resistance and the heat resistance of the resin composition after curing. The research shows that the prepolymer viscosity of the allylbisphenol A is still larger, the process operability is poor, and the influence on the heat resistance of the bismaleimide resin is remarkable if the prepolymer viscosity is too much, and the bismaleimide resin composition provided by the embodiment of the invention has better toughness, impact resistance and heat resistance after being cured by further optimizing the mass parts of each component in the composition. The bismaleimide resin composition of the embodiment of the invention further optimizes the mass ratio of each component in the preparation raw materials of the allylphenol oxygen resin, and more target allylphenol oxygen resin products can be obtained by adopting the mass ratio.
Wherein the flexible side chain modified epoxy resin refers to the side chain of the epoxy resin grafted with a flexible chain segment. The flexible chain segment refers to a chain segment with stronger activity, such as carbon-oxygen bond, carbon-silicon bond, carbon-nitrogen bond, silicon-oxygen bond and the like, and can be grafted with polyether chain, siloxane chain, polyamide and other structures.
In some embodiments, the flexible side chain modified epoxy resin is prepared from raw materials including epoxy resin, isocyanate-terminated polyether and a second catalyst, wherein the ratio of the raw materials is 1:6-7:0.005-0.01.
According to the bismaleimide resin composition provided by the embodiment of the invention, the hydroxyl in the epoxy resin reacts with the isocyanate group on the isocyanate-terminated polyether, so that the polyether flexible chain segment is introduced between the epoxy resin chain segments, and the yield of a target product is higher when the raw material mass ratio is adopted.
In some embodiments, the isocyanate-terminated polyether is prepared by a plurality of methods and can be prepared by various known methods and raw materials. Preferably, the isocyanate-terminated polyether is prepared from toluene-2, 4-diisocyanate and polypropylene glycol; the dosage of toluene-2, 4-diisocyanate and polypropylene glycol satisfies that the molar ratio of-NCO in toluene-2, 4-diisocyanate to-OH in polypropylene glycol is 2:1.
The isocyanate-terminated polyether is formed by the reaction of the-NCO in the toluene-2, 4-diisocyanate and the-OH in the polypropylene glycol, and by adopting the proportion, one-NCO in the toluene-2, 4-diisocyanate molecule can be reacted with the polypropylene glycol, and the other-NCO is reserved and then is reacted with the-OH in the epoxy resin.
Among them, polypropylene glycol is selected from a plurality of types, and depending on the molecular weight of polypropylene glycol, polypropylene glycol may be polypropylene glycol 400, polypropylene glycol 2000, polypropylene glycol 4000, polypropylene glycol 6000, etc. The polypropylene glycol has different molecular weights, different chain lengths and different flexibility, and is grafted on the epoxy resin, when the bismaleimide resin is modified, the network structure formed in the curing process of the bismaleimide resin is different, and the influence on the toughness, the impact resistance and the heat resistance of the bismaleimide resin is different. Preferably, the polypropylene glycol is polypropylene glycol 4000. Experimental study shows that the bismaleimide resin obtained by adopting polypropylene glycol 4000 has better comprehensive properties such as toughness, impact resistance, heat resistance and the like.
In some embodiments, the diallyl phenol is preferably diallyl bisphenol a.
In some embodiments, the epoxy resin is preferably bisphenol a type epoxy resin.
In some embodiments, the first catalyst is preferably a quaternary ammonium salt.
In some embodiments, the second catalyst is preferably dibutyltin dilaurate.
The second aspect of the present invention provides a method for preparing the above bismaleimide resin composition, comprising the steps of:
melting allylphenol oxygen resin, adding bismaleimide resin, prepolymerizing for 10-30min at 130-140 ℃, adding diallyl bisphenol A, and continuing to react for 10-30min at 130-140 ℃ to obtain the bismaleimide resin composition.
In some embodiments, the method of preparing the allylphenoxy resin comprises the steps of:
mixing diallyl phenol, flexible side chain modified epoxy resin and a first catalyst, reacting at 50-70 ℃, continuously monitoring the epoxy value of the product, and stopping the reaction when the epoxy value is less than 0.03 to obtain the allyl phenol oxygen resin.
In some embodiments, the method of preparing the flexible side chain modified epoxy resin comprises the steps of:
mixing epoxy resin, isocyanate-terminated polyether and a second catalyst under the protection of inert gas, and reacting for 1-4 hours at 60-80 ℃ to obtain the flexible side chain modified epoxy resin.
In some embodiments, the method of making the isocyanate-terminated polyether comprises the steps of:
toluene-2, 4-diisocyanate and polypropylene glycol are mixed under the protection of inert gas and react for 1-4 hours at 60-80 ℃ to obtain the isocyanate-terminated polyether.
A third aspect of the present invention provides a fiber-reinforced bismaleimide resin-based composite comprising a fiber-reinforced material and the above-described bismaleimide resin composition.
In some embodiments, the fibrous reinforcement comprises 30% -50% of the mass of the composite.
In some embodiments, the fibrous reinforcement is preferably carbon fibers.
The fourth aspect of the present invention provides a method for preparing the fiber reinforced bismaleimide resin matrix composite, comprising the following steps:
and (3) impregnating the bismaleimide resin composition with a fiber reinforced material to obtain a prepreg, and then paving and laminating the prepreg, and then curing and forming by microwave to obtain the fiber reinforced bismaleimide resin matrix composite material.
The preparation method provided by the embodiment of the invention adopts microwave curing molding, and has the advantages of high microwave curing heating efficiency, uniform heating, accurate and controllable heating process and short production period, so that the curing effect is better, and the mechanical property of the cured composite material is better.
The curing reaction can be completed in a short time at a higher temperature, or can be completed in a long time at a lower temperature, and when the curing reaction is carried out at a higher temperature, the reaction is severe, so that larger internal stress is generated in the cured product; when the curing reaction is carried out at a lower temperature, the reaction is stable, the structure of the cured product is compact, but the later stage of the reaction is easy to cure incompletely. Experiments prove that the gradient heating is adopted, and the gradient heating program is as follows: curing for 0.5-2h at 130-140 ℃, then heating to 150-160 ℃ for curing for 10-14h, and then heating to 180-190 ℃ for curing for 10-14h, so that the toughness, impact resistance and heat resistance of the cured composite material are optimal.
Example 1
The bismaleimide resin composition provided by the embodiment comprises the following components in parts by mass:
100 parts of bismaleimide resin, 40 parts of allylphenoxy resin and 35 parts of diallyl bisphenol A.
The preparation method of the bismaleimide resin composition of the present embodiment includes the following steps:
s1, preparation of isocyanate-terminated polyether, toluene-2, 4-diisocyanate was added to a flask and N was introduced 2 Slowly dripping the polypropylene glycol 4000 while stirring at 70 ℃, and reacting for 2 hours after dripping is finished to obtain isocyanate-terminated polyether, wherein the dosage of the toluene-2, 4-diisocyanate and the polypropylene glycol 4000 satisfies that the molar ratio of-NCO in the toluene-2, 4-diisocyanate to-OH in the polypropylene glycol is 2:1;
s2, preparing flexible side chain modified epoxy resin, adding bisphenol A epoxy resin and isocyanate-terminated polyether into a flask, and introducing N 2 Adding dibutyl tin dilaurate, and reacting for 2 hours at 70 ℃ to obtain flexible side chain modified epoxy resin, wherein the mass ratio of bisphenol A epoxy resin to isocyanate group-terminated polyether to dibutyl tin dilaurate is 1:6.5:0.008;
s3, preparing allylphenol oxygen resin, namely mixing diallyl phenol, flexible side chain modified epoxy resin and a quaternary ammonium salt catalyst, reacting at 60 ℃, continuously monitoring the epoxy value of a product, and stopping the reaction when the epoxy value is less than 0.03 to obtain allylphenol oxygen resin, wherein diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the quaternary ammonium salt catalyst is 1:0.45:0.09;
s4, melting allyl phenol oxygen resin, adding bismaleimide resin, prepolymerizing for 20min at 135 ℃, adding diallyl bisphenol A, and continuing to react for 20min at 135 ℃ to obtain the bismaleimide resin composition.
As shown in fig. 1 and 2, photographs of the bismaleimide resin composition during the preparation process are shown.
The preparation method of the carbon fiber reinforced bismaleimide resin matrix composite material comprises the following steps:
the bismaleimide resin composition is impregnated with carbon fibers to obtain a prepreg, wherein the mass fraction of the carbon fibers in the prepreg is 40%, and then the prepreg is laid and laminated, and then is subjected to microwave curing molding, and a curing gradient heating program is as follows: curing for 1h at 135 ℃, then heating to 155 ℃ for curing for 12h, and then heating to 185 ℃ for curing for 12h to obtain the fiber reinforced bismaleimide resin matrix composite.
Example 2
The bismaleimide resin composition provided by the embodiment comprises the following components in parts by mass:
100 parts of bismaleimide resin, 38 parts of allylphenoxy resin and 38 parts of diallyl bisphenol A.
The preparation method of the bismaleimide resin composition in the embodiment has the same specific steps as those in the embodiment 1, and is distinguished in that in the preparation raw materials of the flexible side chain modified epoxy resin, the mass ratio of bisphenol A epoxy resin, isocyanate terminated polyether and dibutyltin dilaurate is 1:7:0.005; in the preparation raw materials of the allylphenol oxygen resin, diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the quaternary ammonium salt catalyst is 1:0.43:0.1.
The preparation method of the carbon fiber reinforced bismaleimide resin matrix composite of this example is the same as that of example 1.
Example 3
The bismaleimide resin composition provided by the embodiment comprises the following components in parts by mass:
100 parts of bismaleimide resin, 42 parts of allylphenoxy resin and 30 parts of diallyl bisphenol A.
The preparation method of the bismaleimide resin composition in the embodiment has the same specific steps as those in the embodiment 1, and is distinguished in that in the preparation raw materials of the flexible side chain modified epoxy resin, the mass ratio of bisphenol A epoxy resin, isocyanate-terminated polyether and dibutyltin dilaurate is 1:6:0.01; in the preparation raw materials of the allylphenol oxygen resin, diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the quaternary ammonium salt catalyst is 1:0.48:0.08.
The preparation method of the carbon fiber reinforced bismaleimide resin matrix composite of this example is the same as that of example 1.
Example 4
The bismaleimide resin composition provided by the embodiment comprises the following components in parts by mass:
100 parts of bismaleimide resin, 32 parts of allylphenoxy resin and 42 parts of diallyl bisphenol A.
The preparation method of the bismaleimide resin composition of this example is the same as that of example 1, except that in the preparation raw material of allylphenol epoxy resin, diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the quaternary ammonium salt catalyst is 1:0.5:0.05.
The preparation method of the carbon fiber reinforced bismaleimide resin matrix composite of this example is the same as that of example 1.
Example 5
The bismaleimide resin composition provided by the embodiment comprises the following components in parts by mass:
100 parts of bismaleimide resin, 48 parts of allylphenoxy resin and 22 parts of diallyl bisphenol A.
The preparation method of the bismaleimide resin composition of this example is the same as that of example 1, except that in the preparation raw material of allylphenol epoxy resin, diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the quaternary ammonium salt catalyst is 1:0.4:0.15.
The preparation method of the carbon fiber reinforced bismaleimide resin matrix composite of this example is the same as that of example 1.
Example 6
The bismaleimide resin composition of this example was identical to that of example 1 in terms of the remaining components and preparation method, except that polypropylene glycol 400 was used as the polypropylene glycol.
Example 7
The bismaleimide resin composition of this example was identical to that of example 1 in terms of the remaining components and preparation method, except that polypropylene glycol 2000 was used as the polypropylene glycol.
Example 8
The bismaleimide resin composition of this example was identical to that of example 1 in terms of the remaining components and preparation method, except that polypropylene glycol 6000 was used as the polypropylene glycol.
Example 9
The bismaleimide resin composition of this example was prepared in the same manner as in example 1 except that the composition was molded by autoclave curing.
Example 10
The bismaleimide resin composition of this example was identical to example 1 in the components and other steps of the preparation method, except that the gradient-temperature-rising curing procedure was: curing for 2h at 120 ℃, then heating to 140 ℃ for 14h, and then heating to 170 ℃ for 14h.
Example 11
The bismaleimide resin composition of this example was identical to example 1 in the components and other steps of the preparation method, except that the gradient-temperature-rising curing procedure was: curing at 150 ℃ for 0.5h, then heating to 170 ℃ for 10h, and then heating to 200 ℃ for 10h.
Comparative example 1
The bismaleimide resin composition described in this comparative example was identical to example 1 in other components and preparation methods, except that the flexible side chain modified epoxy resin in the starting material was replaced with an equimolar amount of epoxy resin, i.e., the epoxy resin was not modified.
Performance test of carbon fiber reinforced bismaleimide resin matrix composite
The flexural strength and impact strength of the carbon fiber reinforced bismaleimide resin matrix composite obtained in each example were measured, and the experimental results are shown in table 1 below. As can be seen from table 1 below, compared with comparative example 1, the carbon fiber reinforced bismaleimide resin matrix composite obtained in each example of the present invention has significantly improved bending strength and impact strength, which indicates that the flexibility and impact resistance of the bismaleimide resin matrix composite are improved due to the introduction of the flexible groups. Among them, the compositions of examples 1 to 5 are different in the number of parts of each component, examples 1 to 3 are preferred examples, and example 1 is the most preferred example, and has the most preferred bending strength and impact strength. Examples 6, 7 and 8 are different from example 1 in that the molecular weight of polypropylene glycol used is different, and the polypropylene glycol molecular weight of examples 6 and 7 is too low, and the toughness and impact resistance of the composite material are not improved as compared with example 1, while the polypropylene glycol molecular weight of example 8 is too high, and the toughness and impact resistance of the composite material are slightly higher than those of example 1, but the glass transition temperature of the composite material is significantly reduced, which means that the heat resistance is significantly reduced. Example 9 is different from example 1 in that autoclave curing is used, and the toughness and impact resistance of the composite material are not the same as those of example 1. Examples 10 and 11 are different from the gradient temperature-rising curing procedure of example 1, and the toughness and impact resistance of the composite materials of examples 10 and 11 are inferior to those of example 1, indicating that the curing procedure adopted in example 1 is a preferable curing procedure.
TABLE 1
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The bismaleimide resin composition is characterized by comprising the following components in parts by weight:
100 parts of bismaleimide resin, 30-50 parts of allylphenol oxygen resin and 20-45 parts of diallyl bisphenol A;
the preparation raw materials of the allylphenol oxygen resin comprise diallyl phenol, flexible side chain modified epoxy resin and a first catalyst; diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the first catalyst is 1:0.4-0.5:0.05-0.15.
2. The bismaleimide resin composition according to claim 1, comprising the following components in parts by mass:
100 parts of bismaleimide resin, 38-42 parts of allylphenol oxygen resin and 30-38 parts of diallyl bisphenol A;
in the preparation raw materials of the allylphenol oxygen resin, diallyl phenol: flexible side chain modified epoxy resin: the mass ratio of the first catalyst is 1:0.43-0.48:0.08-0.1.
3. The bismaleimide resin composition according to claim 2, wherein:
the preparation raw materials of the flexible side chain modified epoxy resin comprise epoxy resin, isocyanate-terminated polyether and a second catalyst, wherein the ratio of the raw materials is 1:6-7:0.005-0.01.
4. The bismaleimide resin composition according to claim 3 wherein:
the preparation raw materials of the isocyanate-terminated polyether comprise toluene-2, 4-diisocyanate and polypropylene glycol; the dosage of toluene-2, 4-diisocyanate and polypropylene glycol satisfies that the molar ratio of-NCO in toluene-2, 4-diisocyanate to-OH in polypropylene glycol is 2:1.
5. The bismaleimide resin composition according to claim 4 wherein:
the polypropylene glycol is polypropylene glycol 4000.
6. The bismaleimide resin composition according to claim 4 wherein:
the diallyl phenol is diallyl bisphenol A; the epoxy resin is bisphenol A type epoxy resin; the first catalyst is quaternary ammonium salt; the second catalyst is dibutyl tin dilaurate.
7. A method for producing the bismaleimide resin composition according to any one of claims 1 to 6 comprising the steps of:
melting allylphenol oxygen resin, adding bismaleimide resin, prepolymerizing for 10-30min at 130-140 ℃, adding diallyl bisphenol A, and continuing to react for 10-30min at 130-140 ℃ to obtain the bismaleimide resin composition.
8. A fiber-reinforced bismaleimide resin matrix composite is characterized in that:
comprising a fiber reinforcement and the bismaleimide resin composition according to any one of claims 1 to 6.
9. A method for preparing the fiber reinforced bismaleimide resin matrix composite according to claim 8 comprising the steps of:
and (3) impregnating the bismaleimide resin composition with a fiber reinforced material to obtain a prepreg, and then paving and laminating the prepreg, and then curing and forming by microwave to obtain the fiber reinforced bismaleimide resin matrix composite material.
10. The method of manufacturing according to claim 9, wherein:
the microwave curing and forming adopts gradient heating and curing, and the gradient heating program is as follows: curing at 130-140 deg.C for 0.5-2 hr, then heating to 150-160 deg.C for 10-14 hr, and heating to 180-190 deg.C for 10-14 hr.
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