CN114213631B - Resin toughening composition, resin toughening modifier, modified bismaleimide resin composition and cured product - Google Patents
Resin toughening composition, resin toughening modifier, modified bismaleimide resin composition and cured product Download PDFInfo
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- CN114213631B CN114213631B CN202111555082.2A CN202111555082A CN114213631B CN 114213631 B CN114213631 B CN 114213631B CN 202111555082 A CN202111555082 A CN 202111555082A CN 114213631 B CN114213631 B CN 114213631B
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- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical class 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 201
- 229920005989 resin Polymers 0.000 title claims abstract description 160
- 239000011347 resin Substances 0.000 title claims abstract description 160
- 239000003607 modifier Substances 0.000 title claims abstract description 91
- 239000011342 resin composition Substances 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 73
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims abstract description 54
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 19
- 238000007259 addition reaction Methods 0.000 claims abstract description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 43
- -1 diallyl phenyl compound Chemical class 0.000 claims description 27
- 229920005992 thermoplastic resin Polymers 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 15
- 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 description 13
- 239000004695 Polyether sulfone Substances 0.000 claims description 11
- 229920006393 polyether sulfone Polymers 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- LQZUVUANAHQVJU-UHFFFAOYSA-N 4-nonan-5-yl-1-oxidopyridin-1-ium Chemical compound CCCCC(CCCC)C1=CC=[N+]([O-])C=C1 LQZUVUANAHQVJU-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 abstract description 9
- 230000009286 beneficial effect Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 4
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 59
- 238000001816 cooling Methods 0.000 description 31
- 238000003756 stirring Methods 0.000 description 25
- 238000010438 heat treatment Methods 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012153 distilled water Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000005266 casting Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 239000012467 final product Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 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 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007676 flexural strength test Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
- C08G59/245—Di-epoxy compounds carbocyclic aromatic
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a resin toughening composition, a resin toughening modifier, a modified bismaleimide resin composition and a cured product. The resin toughening composition comprises the following components in percentage by mass: 30-55% of diphenylmethane bismaleimide, 15-30% of diaminodiphenylmethane and 20-40% of bisphenol A diglycidyl ether. The molecular chain of the diphenylmethane bismaleimide is expanded by utilizing the addition reaction of the diphenylmethane bismaleimide and the diaminodiphenylmethane, and the active hydrogen on the amino group of the addition product is utilized to carry out ring-opening reaction with the epoxy group in the bisphenol A diglycidyl ether, so that the flexible group is introduced. The toughening composition can reduce the crosslinking density of the bismaleimide resin condensate, and the flexible chain can rotate to play a role in enhancing the toughness of the resin, and meanwhile, the toughening composition can also improve the mechanical property of the resin, thereby being beneficial to expanding the use performance and the use range.
Description
Technical Field
The invention relates to the technical field of bismaleimide resin, in particular to a resin toughening composition, a resin toughening modifier, a modified bismaleimide resin composition and a cured product.
Background
The bismaleimide resin is a high-performance thermosetting resin widely applied in the field of aerospace, has higher glass transition temperature, good wet heat resistance, electrical insulation performance, flame retardance, radiation resistance and mechanical performance, and becomes a main competitor in the field of thermosetting materials. However, the rigid structure and the large crosslinking density of the bismaleimide resin enable polymer chains to be orderly piled up due to the existence of polar carbonyl groups, so that the energy dissipation probability is reduced, the toughness of the bismaleimide resin is poor, and the usability and the application range of the bismaleimide resin are reduced to a certain extent.
In view of this, the present invention has been made.
Disclosure of Invention
The invention mainly aims to provide a resin toughening composition, a resin toughening modifier, a modified bismaleimide resin composition and a cured product, so as to improve the technical problems that the toughness of the bismaleimide resin is poor, and the usability and the application range of the bismaleimide resin are reduced to a certain extent.
In order to achieve the above object, according to one aspect of the present invention, there is provided a resin toughening composition comprising, in mass percent: 30-55% of diphenylmethane bismaleimide, 15-30% of diaminodiphenylmethane and 20-40% of bisphenol A diglycidyl ether.
Further, the resin toughening composition includes, in mass percent: 45% -50% of diphenylmethane bismaleimide, 20% -25% of diaminodiphenylmethane and 25% -30% of bisphenol A diglycidyl ether.
According to another aspect of the present invention, there is provided a resin toughening modifier prepared using the above resin toughening composition.
Further, the preparation method of the resin toughening modifier comprises the following steps: step S1, performing an addition reaction on diphenylmethane bismaleimide and diaminodiphenylmethane to obtain an addition product system; s2, carrying out ring-opening reaction on an addition product in the addition product system and bisphenol A diglycidyl ether to obtain the resin toughening modifier.
Further, step S1 includes: A. respectively dissolving diphenylmethane bismaleimide and diaminodiphenylmethane in a solvent to obtain a diphenylmethane bismaleimide solution and a diaminodiphenylmethane solution; B. mixing diphenylmethane bismaleimide solution and diaminodiphenylmethane solution for addition reaction to obtain an addition product system, wherein the temperature of the addition reaction is preferably 80-90 ℃ and the time is 25-40min; preferably, the solvents dissolving diphenylmethane bismaleimide and diaminodiphenylmethane each independently comprise at least one of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, acetonitrile or N-methylpyrrolidone.
Further, the temperature of the ring-opening reaction is 90-100 ℃ and the time is 40-50min; further, it is preferable that step S2 further comprises preheating bisphenol A glycidyl ether at 80-90℃for 25-40min before the ring-opening reaction is performed.
According to a third aspect of the present invention, there is provided a modified bismaleimide resin composition comprising bismaleimide and a toughening modifier which is the resin toughening modifier provided in the second aspect.
Further, the modified bismaleimide resin composition also includes a diallyl phenyl compound and a thermoplastic resin. Further, the bismaleimide resin composition includes, in mass percent: 10-25% of diallyl phenyl compound, 35-35% of bismaleimide, 5-25% of thermoplastic resin and 5-20% of toughening modifier. Further, the bismaleimide resin composition includes, in mass percent: 15-25% of diallyl phenyl compound, 40-50% of bismaleimide, 10-20% of thermoplastic resin and 5-15% of toughening modifier.
Further, the diallyl phenyl compound comprises at least one of diallyl bisphenol a, bisphenol a bis-diallyl ether, or diallyl bisphenol S. Further, the thermoplastic resin includes at least one of polyimide, polyethersulfone, or polyetherimide. Further, the bismaleimide may include at least one of N, N- (4, 4-methylenediphenyl) bismaleimide or N, N- (4-methyl-1, 3-phenylene) bismaleimide, N- (1, 4-phenylene) bismaleimide.
Further, the bismaleimide resin composition is a mixture, and the process of forming the mixture includes: sequentially adding bismaleimide, thermoplastic resin and toughening modifier into a diallyl phenyl compound and mixing to obtain a mixture; preferably, the diallyl phenyl compound is preheated at 85-90 ℃ for 25-40min, and then bismaleimide, thermoplastic resin and toughening modifier are added in sequence.
According to a fourth aspect of the present invention, there is provided a modified bismaleimide resin cured product obtained by curing the modified bismaleimide resin composition provided in the third aspect.
By applying the technical scheme of the invention, the invention has at least the following beneficial effects:
the bismaleimide resin toughening modifier provided by the invention expands the molecular chain of diphenylmethane bismaleimide by utilizing the addition reaction of the diphenylmethane bismaleimide and diaminodiphenylmethane, and then utilizes the ring-opening reaction of active hydrogen on amino of an addition product and epoxy groups in bisphenol A diglycidyl ether to introduce flexible groups. Therefore, when the modified bismaleimide resin is added into a bismaleimide resin system as a toughening modifier, the crosslinking density of a bismaleimide resin cured product can be reduced, a flexible chain can rotate to absorb external energy, the toughness of the resin is enhanced, the mechanical property of the resin can be improved, and the use performance and the use range of the bismaleimide resin can be enlarged.
Detailed Description
It should be noted that, in the case of no conflict, the embodiments and features in the embodiments may be combined with each other. The present invention will be described in detail with reference to examples.
As analyzed in the background of the present application, the presence of polar carbonyl groups, while allowing for orderly stacking of polymer chains, results in lower energy dissipation probability, resulting in poorer toughness of the bismaleimide resin, and, to some extent, reduced performance and range of use of the bismaleimide resin due to the rigid structure and large crosslink density of the bismaleimide resin. In order to solve this problem, the present application provides a resin toughening composition, a resin toughening modifier, a modified bismaleimide resin, and a cured product.
In one exemplary embodiment of the present application, there is provided a resin toughening composition comprising, in mass percent: 30-55% of diphenylmethane bismaleimide, 15-30% of diaminodiphenylmethane and 20-40% of bisphenol A glycidyl ether.
Bisphenol A glycidyl ether has double epoxy functional groups, and is favorable for ring-opening reaction with other substances.
According to the resin toughening composition provided by the application, the diphenylmethane bismaleimide can undergo an addition reaction with diaminodiphenylmethane to expand a molecular chain, then an active hydrogen on an amino group of an addition product can be utilized to undergo a ring-opening reaction with an epoxy group in bisphenol A diglycidyl ether, and a flexible group is introduced to generate the resin toughening modifier. After the resin toughening modifier is added into the bismaleimide resin system, the crosslinking density of the bismaleimide resin cured product can be reduced, external energy can be absorbed by utilizing rotation of a flexible chain, the toughness of the resin cured product is enhanced, and meanwhile, the mechanical property is improved, so that the use performance and the use range of the bismaleimide resin are favorably enlarged.
Typically, but not by way of limitation, the content of diphenylmethane bismaleimide in the resin toughening composition is, for example, 30%, 35%, 40%, 45%, 50% or 55% by mass; the diaminodiphenylmethane content is, for example, 15%, 18%, 20%, 22%, 25%, 28% or 30%; the content of bisphenol A diglycidyl ether is, for example, 20%, 25%, 30%, 35% or 40%.
In some embodiments of the present application, in the resin toughening composition, when the content of diphenylmethane bismaleimide is 45% -50% by mass, the content of diaminodiphenylmethane is 20% -25% and the content of bisphenol a diglycidyl ether is 25% -30%, the toughening performance of the resin toughening modifier generated after the reaction of the raw materials is more excellent.
In another exemplary embodiment of the present application, a resin toughening modifier is provided, which is prepared from the above-described resin toughening composition.
According to the resin toughening modifier, the molecular chain of the diphenylmethane bismaleimide is expanded through the diaminodiphenylmethane, and the flexible group is introduced through the bisphenol A diglycidyl ether, so that after the resin toughening modifier is added into a bismaleimide resin system, the crosslinking density of a cured product can be reduced, and the toughness and mechanical strength of the cured product can be improved.
In some embodiments of the present application, a method of preparing a resin toughening modifier includes: step S1, performing an addition reaction on diphenylmethane bismaleimide and diaminodiphenylmethane to obtain an addition product system; and S2, carrying out ring-opening reaction on an addition product in the addition product system and bisphenol A diglycidyl ether to obtain the resin toughening modifier.
In the step S1, diaminodiphenyl methane and diphenyl methane bismaleimide undergo an addition reaction, an amino group with active hydrogen is introduced into an addition product while the molecular chain of the diphenyl methane bismaleimide is expanded, and the subsequent reaction of the active hydrogen on the amino group and a substance containing a flexible chain is facilitated, so that a flexible group is introduced.
In some preferred embodiments of the present application, step S1 comprises: A. respectively dissolving diphenylmethane bismaleimide and diaminodiphenylmethane in a solvent to obtain a diphenylmethane bismaleimide solution and a diaminodiphenylmethane solution; B. and mixing the diphenylmethane bismaleimide solution and the diaminodiphenylmethane solution for addition reaction to obtain an addition product system. And respectively dissolving the diphenylmethane bismaleimide and the diaminodiphenylmethane in the solvent to form respective solutions, so that the addition reaction efficiency and the product yield of the diphenylmethane bismaleimide and the diaminodiphenylmethane in a liquid phase system are improved.
In the above step A, the solvent for dissolving diphenylmethane bismaleimide and diaminodiphenylmethane may be the same or different, so long as diphenylmethane bismaleimide or diaminodiphenylmethane is soluble.
Preferably, the solvents for dissolving diphenylmethane bismaleimide and diaminodiphenylmethane each independently include, but are not limited to, any one or a mixture of several of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, acetonitrile or N-methylpyrrolidone.
In some embodiments, in the step B, the addition reaction is performed more fully at a temperature of 80-90 ℃ for 25-40min, so that the efficiency of the addition reaction is improved.
Typically, but not by way of limitation, the temperature of the addition reaction is, for example, 80 ℃, 82 ℃, 85 ℃, 88 ℃, or 90 ℃ for a period of time such as 25min, 28min, 30min, 32min, 35min, 38min, or 40min.
After the addition product system is obtained, the addition product system can be directly utilized to carry out the next ring-opening reaction with bisphenol A diglycidyl ether. In order to reduce the formation of by-products and to increase the yield of the desired product, it is preferable to purify the addition product in the addition product system, for example, step B further comprises mixing the addition product system with water, crystallizing, solid-liquid separating and drying to obtain the addition product.
The manner of crystallization includes, but is not limited to, the following: adding the addition product system into distilled water, and cooling and crystallizing at 20-30deg.C.
Preferably, the water includes, but is not limited to distilled water, deionized water, or purified water, and the solid-liquid separation includes, but is not limited to, filtration.
In the step S2, the active hydrogen on the amino of the addition product and the epoxy group in the bisphenol A diglycidyl ether are utilized to carry out ring-opening reaction, so that a flexible group is introduced into the resin toughening modifier, and the toughness and mechanical property of the bismaleimide resin can be effectively enhanced after the resin toughening agent is added into the bismaleimide resin system.
In some embodiments of the present application, in step S2, when the temperature of the ring-opening reaction is 90-100 ℃ and the time is 40-50min, the ring-opening reaction is more fully performed, and the efficiency of the ring-opening reaction is improved.
Typically, but not by way of limitation, the temperature of the ring-opening reaction is, for example, 90 ℃, 92 ℃, 95 ℃, 98 ℃ or 100 ℃ for a period of time such as 40min, 42min, 45min, 48min or 50min.
Preferably, in step S2, before the ring-opening reaction, the method further comprises preheating bisphenol a glycidyl ether at 80-90 ℃ for 25-40min, which is more beneficial to improving the ring-opening reaction efficiency.
Typically, but not by way of limitation, the bisphenol A glycidyl ether is preheated at a temperature of, for example, 80 ℃, 82 ℃, 85 ℃, 88 ℃ or 90 ℃ for a period of, for example, 25, 28, 30, 32, 35 or 40 minutes.
In a third exemplary embodiment of the present application, a modified bismaleimide resin composition is provided that includes bismaleimide and a toughening modifier that is the resin toughening modifier provided in the second exemplary embodiment described above.
According to the bismaleimide resin composition, the resin toughening modifier is introduced into the bismaleimide resin, so that the crosslinking density of a bismaleimide resin cured product can be reduced on the basis of guaranteeing the moisture and heat resistance of the bismaleimide resin, the toughness and the mechanical property can be enhanced, and the use performance and the use range of the bismaleimide resin can be enlarged.
Preferably, the bismaleimides include, but are not limited to, N- (4, 4-methylenediphenyl) bismaleimide or any one or a mixture of N, N- (4-methyl-1, 3-phenylene) bismaleimide and N, N- (1, 4-phenylene) bismaleimide.
In some embodiments of the present application, the modified bismaleimide resin composition further includes a diallyl benzene compound and a thermoplastic resin.
Allyl compounds are added into the modified bismaleimide resin composition for copolymerization modification, so that the heat resistance and mechanical properties of the bismaleimide resin cured product are improved. The thermoplastic resin generally has outstanding toughness, molecular chains are in a linear structure and can be softened and flow after being heated and pressurized, the thermoplastic resin is added into the modified bismaleimide resin composition, the aggregation state structure of the bismaleimide can be changed on the premise of keeping the mechanical property and the heat resistance of the bismaleimide resin, a macroscopically uniform and microscopically two-phase sea-island structure is formed, further development of cracks is effectively prevented, meanwhile, the thermoplastic resin can be synergistically toughened with the resin toughening modifier, and the toughness and the mechanical strength are improved on the basis of ensuring the heat resistance of a maleimide resin system.
The above diallyl phenyl compound and the thermoplastic resin may each be a corresponding material commonly used in the modification of bismaleimide resins, such as diallyl phenyl compounds including, but not limited to, any one or a mixture of diallyl bisphenol A, bisphenol A bis-diallyl ether, or diallyl bisphenol S. Such as
Thermoplastic resins include, but are not limited to, any one or a mixture of several of polyimide, polyethersulfone, or polyetherimide.
In some preferred embodiments of the present application, the bismaleimide resin composition includes, in mass percent: 10-25% of diallyl phenyl compound, 35-50% of bismaleimide, 5-25% of thermoplastic resin and 5-20% of toughening modifier.
The diallyl phenyl compound, the bismaleimide, the thermoplastic resin and the toughening modifier are matched with each other according to a specific mass ratio, so that the prepared maleimide resin can obviously improve the toughness and the mechanical strength on the basis of ensuring the heat resistance, and the use performance and the use range of the bismaleimide resin are favorably enlarged.
Typically, but not by way of limitation, the content of the diallyl compound in the bismaleimide resin composition is, for example, 10%, 12%, 15%, 18%, 20%, 22% or 25%, the content of bismaleimide is, for example, 35%, 38%, 40%, 42%, 45%, 48% or 50%, the content of the thermoplastic resin is, for example, 5%, 8%, 10%, 12%, 15%, 20%, 22% or 25%, and the content of the toughening modifier is, for example, 5%, 8%, 10%, 12%, 15%, 18% or 20%.
Preferably, when the bismaleimide resin composition comprises 15-25% of diallyl phenyl compound, 40-50% of bismaleimide, 10-20% of thermoplastic resin and 5-15% of toughening modifier by mass percentage, the raw materials are mutually cooperated, and the prepared bismaleimide resin is more excellent in heat resistance, toughness and mechanical property.
The components in the modified bismaleimide resin composition can be independently packaged and sold in combination, and the components can exist relatively stably at room temperature, so the modified bismaleimide resin composition can also be a mixture, and the process for forming the mixture comprises the following steps: the bismaleimide, the thermoplastic resin and the toughening modifier are sequentially added into the diallyl phenyl compound to be mixed, so that the mixture is obtained.
Preferably, the diallyl phenyl compound is preheated at 85-90 ℃ for 25-40min, and then bismaleimide, thermoplastic resin and toughening modifier are sequentially added, so that more uniform mixing of the raw materials is facilitated.
Typically, but not by way of limitation, the diallyl phenyl compound is preheated at a temperature of, e.g., 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃ or 90 ℃ for a period of, e.g., 25, 28, 30, 32, 35, 38 or 40 minutes.
In a fourth exemplary embodiment of the present application, a bismaleimide resin cured product is provided that is cured from the modified bismaleimide resin composition provided in the third exemplary embodiment of the present application.
In the bismaleimide resin cured product provided by the application, the introduction of the toughening modifier is beneficial to reducing the crosslinking density of the cured product, and is beneficial to absorbing external energy through a flexible chain in the toughening modifier, so that the toughness is enhanced; the introduction of the allyl compound is beneficial to improving the heat resistance and mechanical properties of the cured product; the introduction of the thermoplastic resin is beneficial to changing the aggregation state structure of the bismaleimide, forming a macroscopically uniform and microscopically bidirectional structure, and preventing the further development of cracks.
The bismaleimide resin condensate provided by the application is matched with the toughening modifier through the diallyl phenyl compound, the bismaleimide, the thermoplastic resin and the toughening modifier, so that the toughness and the mechanical strength are obviously improved on the basis of reducing the crosslinking density and guaranteeing the heat resistance, and the use performance and the use range of the bismaleimide resin are favorably enlarged.
In some embodiments of the present application, a method of preparing a modified bismaleimide resin cured product includes: and vacuumizing the modified bismaleimide resin composition to remove bubbles, and pouring and curing to obtain a modified bismaleimide resin cured product.
Preferably, the casting solidification process comprises four stages, wherein the first stage is at 145-155 ℃, the temperature is kept for 55-65min, then the temperature is raised to the second stage, the temperature is kept for 55-65min at 175-185 ℃, the temperature is raised to the third stage, the temperature is kept for 55-65min at 195-205 ℃, finally the temperature is raised to the fourth stage, the temperature is kept for 110-130min at 225-235 ℃, and the modified bismaleimide resin condensate is obtained after cooling.
In an exemplary embodiment of the present application, the curing process is performed as follows: the first stage is heat-preserving for 1h at 150 ℃, then the second stage is heat-preserving for 1h at 180 ℃, then the third stage is heat-preserving for 1h at 200 ℃, finally the fourth stage is heat-preserving for 2h at 230 ℃, and the modified bisimide resin condensate is obtained after cooling.
The cooling mode is not limited, and includes but is not limited to air cooling, water cooling or natural cooling.
The advantageous effects of the present application will be further described below in conjunction with examples and comparative examples.
Example 1
The embodiment provides a resin toughening modifier, which is prepared by the following steps:
(1) 30g of diphenylmethane bismaleimide was dissolved in 200mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 30g of diaminodiphenylmethane were dissolved in 250mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, cooling at 20-30deg.C for crystallization, filtering, and drying to obtain the final product.
(2) Heating 40g bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Example 2
The embodiment provides a resin toughening modifier, which is prepared by the following steps:
(1) 55g of diphenylmethane bismaleimide was dissolved in 400mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 15g of diaminodiphenylmethane were dissolved in 130mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, cooling at 20-30deg.C for crystallization, filtering, and drying to obtain the final product.
(2) Heating 30g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding an addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Example 3
The embodiment provides a resin toughening modifier, which is prepared by the following steps:
(1) 50g of diphenylmethane bismaleimide was dissolved in 400mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 30g of diaminodiphenylmethane were dissolved in 250mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, cooling at 20-30deg.C for crystallization, filtering, and drying to obtain the final product.
(2) Heating 20g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding an addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Example 4
The embodiment provides a resin toughening modifier, which is prepared by the following steps:
(1) 45g of diphenylmethane bismaleimide was dissolved in 300mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 25g of diaminodiphenylmethane were dissolved in 250mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, cooling at 20-30deg.C for crystallization, filtering, and drying to obtain the final product.
(2) Heating 30g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding an addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Example 5
The embodiment provides a resin toughening modifier, which is prepared by the following steps:
(1) 50g of diphenylmethane bismaleimide was dissolved in 400mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 25g of diaminodiphenylmethane were dissolved in 250mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, cooling at 20-30deg.C for crystallization, filtering, and drying to obtain the final product.
(2) Heating 25g bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Example 6
The embodiment provides a resin toughening modifier, which is prepared by the following steps:
(1) 50g of diphenylmethane bismaleimide was dissolved in 400mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 20g of diaminodiphenylmethane was dissolved in 200mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, cooling at 20-30deg.C for crystallization, filtering, and drying to obtain the final product.
(2) Heating 30g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding an addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Example 7
The embodiment provides a resin toughening modifier, which is prepared by the following steps:
(1) 48g of diphenylmethane bismaleimide was dissolved in 350mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 24g of diaminodiphenylmethane were dissolved in 250mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, cooling at 20-30deg.C for crystallization, filtering, and drying to obtain the final product.
(2) Heating 28g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding an addition product, heating at 90-100 ℃ for reaction for 40-50min, and cooling to obtain the resin toughening modifier.
Comparative example 1
The comparative example provides a resin toughening modifier which is different from example 7 in that in the step (1), hexamethylenediamine is used for replacing diaminodiphenylmethane, and the rest of raw materials and the preparation method are the same as example 7, and are not repeated here.
Comparative example 2
The comparative example provides a resin toughening modifier which is different from example 7 in that adipic acid diglycidyl ether is used to replace bisphenol a diglycidyl ether in step (2), and the rest of raw materials and preparation methods are the same as example 7, and are not described in detail herein.
Comparative example 3
The comparative example provides a resin toughening modifier, which is prepared by the following steps:
(1) 48g of diphenylmethane bismaleimide was dissolved in 350mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 5g of diaminodiphenylmethane was dissolved in 50mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, crystallizing, filtering, and drying to obtain addition product.
(2) Heating 47g bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Comparative example 4
The comparative example provides a resin toughening modifier, which is prepared by the following steps:
(1) 48g of diphenylmethane bismaleimide was dissolved in 350mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 40g of diaminodiphenylmethane was dissolved in 400mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, crystallizing, filtering, and drying to obtain addition product.
(2) Heating 12g bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Comparative example 5
The comparative example provides a resin toughening modifier, which is prepared by the following steps:
(1) 20g of diphenylmethane bismaleimide was dissolved in 150mL of N, N-dimethylacetamide and stirred well to dissolve the diphenylmethane bismaleimide completely in the N, N-dimethylacetamide. 40g of diaminodiphenylmethane was dissolved in 400mLN, N-dimethylacetamide and stirred well to dissolve the diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the above two solutions, stirring at 80-90deg.C for 30min, pouring the above solution into distilled water after the reaction, crystallizing, filtering, and drying to obtain addition product.
(2) Heating 30g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding an addition product, heating at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Example 8
The embodiment provides a modified bismaleimide resin condensate, which is prepared according to the following steps:
(1) 50g of diallyl bisphenol A is added into a three-neck flask, the temperature is raised to 90 ℃, 100g of N, N- (1, 4-phenylene) bismaleimide is added under stirring, the mixture is stirred and dissolved into homogeneous phase, 32g of polyethersulfone and 18g of the resin toughening modifier provided in the example 1 are added, and the mixture is stirred uniformly to obtain a modified bismaleimide resin composition;
(2) Vacuumizing the modified bismaleimide resin composition to remove bubbles, and solidifying the modified bismaleimide resin composition according to the following process after casting: the first stage is heat-preserving for 1h at 150 ℃, then the second stage is heat-preserving for 1h at 180 ℃, then the third stage is heat-preserving for 1h at 200 ℃, finally the fourth stage is heat-preserving for 2h at 230 ℃, and the modified bisimide resin condensate is obtained after cooling.
Examples 9 to 14
Examples 9-14 each provide a modified bismaleimide resin cured product that differs from example 8 in that the resin toughening modifiers provided in example 1 are replaced with the resin toughening modifiers provided in examples 2-7, respectively.
Example 15
The embodiment provides a modified bismaleimide resin condensate, which is prepared according to the following steps:
(1) Adding 46g of diallyl bisphenol A into a three-neck flask, heating to 90 ℃, adding 97g of N, N- (4, 4-methylenediphenyl) bismaleimide under stirring, stirring and dissolving to be homogeneous phase, adding 36g of polyimide, 21g of the resin toughening modifier provided in the example 7, and stirring uniformly to obtain a modified bismaleimide resin composition;
(2) Vacuumizing the modified bismaleimide resin composition to remove bubbles, and solidifying the modified bismaleimide resin composition according to the following process after casting: the first stage is heat-preserving for 1h at 150 ℃, then the second stage is heat-preserving for 1h at 180 ℃, then the third stage is heat-preserving for 1h at 200 ℃, finally the fourth stage is heat-preserving for 2h at 230 ℃, and the modified bisimide resin condensate is obtained after cooling.
Example 16
The embodiment provides a modified bismaleimide resin condensate, which is prepared according to the following steps:
(1) Adding 47g of diallyl bisphenol A into a three-neck flask, heating to 90 ℃, adding 94g of N, N- (1, 4-phenylene) bismaleimide under stirring, stirring and dissolving to be homogeneous phase, adding 41g of polyimide and 18g of the resin toughening modifier provided in the example 7, and stirring uniformly to obtain a modified bismaleimide resin composition;
(2) Vacuumizing the modified bismaleimide resin composition to remove bubbles, and solidifying the modified bismaleimide resin composition according to the following process after casting: the first stage is heat-preserving for 1h at 150 ℃, then the second stage is heat-preserving for 1h at 180 ℃, then the third stage is heat-preserving for 1h at 200 ℃, finally the fourth stage is heat-preserving for 2h at 230 ℃, and the modified bisimide resin condensate is obtained after cooling.
Example 17
The embodiment provides a modified bismaleimide resin condensate, which is prepared according to the following steps:
(1) 50g of diallyl bisphenol A is added into a three-neck flask, the temperature is raised to 90 ℃, 100g of N, N- (1, 4-phenylene) bismaleimide is added under stirring, the mixture is stirred and dissolved into homogeneous phase, then 10g of polyethersulfone and 40g of the resin toughening modifier provided in the example 1 are added, and the mixture is stirred uniformly to obtain a modified bismaleimide resin composition;
(2) Vacuumizing the modified bismaleimide resin composition to remove bubbles, and solidifying the modified bismaleimide resin composition according to the following process after casting: the first stage is heat-preserving for 1h at 150 ℃, then the second stage is heat-preserving for 1h at 180 ℃, then the third stage is heat-preserving for 1h at 200 ℃, finally the fourth stage is heat-preserving for 2h at 230 ℃, and the modified bisimide resin condensate is obtained after cooling.
Example 18
The embodiment provides a modified bismaleimide resin condensate, which is prepared according to the following steps:
(1) Adding 20g of diallyl bisphenol A into a three-neck flask, heating to 90 ℃, adding 100g of N, N- (1, 4-phenylene) bismaleimide under stirring, stirring and dissolving to be homogeneous phase, adding 50g of polyethersulfone and 30g of the resin toughening modifier provided in the example 1, and stirring uniformly to obtain a modified bismaleimide resin composition;
(2) Vacuumizing the modified bismaleimide resin composition to remove bubbles, and solidifying the modified bismaleimide resin composition according to the following process after casting: the first stage is heat-preserving for 1h at 150 ℃, then the second stage is heat-preserving for 1h at 180 ℃, then the third stage is heat-preserving for 1h at 200 ℃, finally the fourth stage is heat-preserving for 2h at 230 ℃, and the modified bisimide resin condensate is obtained after cooling.
Example 19
The embodiment provides a modified bismaleimide resin condensate, which is prepared according to the following steps:
(1) 50g of diallyl bisphenol A is added into a three-neck flask, the temperature is raised to 90 ℃, 80g of N, N- (1, 4-phenylene) bismaleimide is added under stirring, the mixture is stirred and dissolved into homogeneous phase, 40g of polyethersulfone and 30g of the resin toughening modifier provided in the example 1 are added, and the mixture is stirred uniformly to obtain a modified bismaleimide resin composition;
(2) Vacuumizing the modified bismaleimide resin composition to remove bubbles, and solidifying the modified bismaleimide resin composition according to the following process after casting: the first stage is heat-preserving for 1h at 150 ℃, then the second stage is heat-preserving for 1h at 180 ℃, then the third stage is heat-preserving for 1h at 200 ℃, finally the fourth stage is heat-preserving for 2h at 230 ℃, and the modified bisimide resin condensate is obtained after cooling.
Example 20
The embodiment provides a modified bismaleimide resin condensate, which is prepared according to the following steps:
(1) Adding 30g of diallyl bisphenol A into a three-neck flask, heating to 90 ℃, adding 100g of N, N- (1, 4-phenylene) bismaleimide under stirring, stirring and dissolving into a homogeneous phase, adding 40g of polyethersulfone, and 30g of the resin toughening modifier provided in the example 1, and stirring uniformly to obtain a modified bismaleimide resin composition;
(2) Vacuumizing the modified bismaleimide resin composition to remove bubbles, and solidifying the modified bismaleimide resin composition according to the following process after casting: the first stage is heat-preserving for 1h at 150 ℃, then the second stage is heat-preserving for 1h at 180 ℃, then the third stage is heat-preserving for 1h at 200 ℃, finally the fourth stage is heat-preserving for 2h at 230 ℃, and the modified bisimide resin condensate is obtained after cooling.
Example 21
This comparative example provides a modified bismaleimide resin cured product differing from example 14 in that in step (1), the amount of diallyl bisphenol A is 10g, the amount of N, N- (1, 4-phenylene) bismaleimide is 100g, the amount of polyethersulfone is 40g, the amount of resin toughening modifier is 50g, and the remaining steps are the same as in example 14, and are not repeated here.
Example 22
This comparative example provides a modified bismaleimide resin cured product differing from example 14 in that in step (1), the amount of diallyl bisphenol A is 40g, the amount of N, N- (1, 4-phenylene) bismaleimide is 100g, the amount of polyethersulfone is 60g, the amount of resin toughening modifier is 5g, and the remaining steps are the same as in example 14, and are not repeated here.
Example 23
The present embodiment provides a modified bismaleimide resin cured product, which is different from embodiment 14 in that polyether sulfone is not added in the process of preparing the modified bismaleimide resin composition in the step (1), and the other raw materials and the preparation method are the same as embodiment 14, and are not repeated herein.
Example 24
The present example provides a modified bismaleimide resin cured product, which is different from example 14 in that no diallyl bisphenol a is added in the process of preparing the modified bismaleimide resin composition in step (1), and the other raw materials and the preparation method are the same as example 14, and are not described herein.
Comparative examples 6 to 10
Comparative examples 6 to 10 respectively provide a modified bismaleimide resin cured product which is different from example 14 in that the resin toughening modifiers provided in example 7 are replaced with the resin toughening modifiers provided in comparative examples 1 to 5, respectively.
The modified bismaleimide resin cured products provided in the above examples and comparative examples were respectively subjected to impact strength and flexural strength tests, and the results are shown in the following table 1, wherein the impact strength is according to the test standard GB/T2567-2008 and the flexural strength is according to the test standard ASTMD7264.
Table 1 table of the strength data of the cured modified bismaleimide resin provided in examples and comparative examples
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
according to the maleimide resin condensate, the resin toughening modifier formed by copolymerizing the diphenylmethane bismaleimide, the diaminodiphenylmethane and the bisphenol A diglycidyl ether is introduced into the bismaleimide resin system, and the diallyl phenyl compound, the bismaleimide, the thermoplastic resin and the toughening modifier are matched with each other, so that the crosslinking density is reduced, the heat resistance is ensured, the toughness and the mechanical strength are obviously improved, and the use performance and the use range of the bismaleimide resin are enlarged.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. The resin toughening modifier is characterized by being prepared from a resin toughening composition; the resin toughening composition comprises the following components in percentage by mass: 30% -55% of diphenylmethane bismaleimide, 15% -30% of diaminodiphenylmethane and 20% -40% of bisphenol A diglycidyl ether; the preparation method of the resin toughening modifier comprises the following steps:
step S1, carrying out an addition reaction on the diphenylmethane bismaleimide and the diaminodiphenylmethane to obtain an addition product system; the temperature of the addition reaction is 80-90 ℃ and the time is 25-40min;
s2, carrying out ring-opening reaction on an addition product in the addition product system and the bisphenol A diglycidyl ether to obtain the resin toughening modifier; the temperature of the ring-opening reaction is 90-100 ℃ and the time is 40-50min.
2. The resin toughening modifier according to claim 1, wherein the resin toughening composition comprises, in mass percent: 45% -50% of diphenylmethane bismaleimide, 20% -25% of diaminodiphenylmethane and 25% -30% of bisphenol A diglycidyl ether.
3. The resin toughening modifier according to claim 2, wherein the step S1 comprises:
A. respectively dissolving the diphenylmethane bismaleimide and the diaminodiphenylmethane in a solvent to obtain a diphenylmethane bismaleimide solution and a diaminodiphenylmethane solution;
B. and mixing the diphenylmethane bismaleimide solution and the diaminodiphenylmethane solution to perform the addition reaction, so as to obtain the addition product system.
4. The resin toughening modifier according to claim 3, wherein the solvent dissolving the diphenylmethane bismaleimide and the diaminodiphenylmethane each independently comprises at least one of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, acetonitrile, or N-methylpyrrolidone.
5. The resin toughening modifier according to claim 1, wherein the step S2 further comprises preheating the bisphenol a diglycidyl ether at 80-90 ℃ for 25-40min before the ring-opening reaction is performed.
6. A modified bismaleimide resin composition comprising a bismaleimide and a toughening modifier, wherein the toughening modifier is the resin toughening modifier of any one of claims 1 to 5.
7. The modified bismaleimide resin composition according to claim 6, wherein the modified bismaleimide resin composition further comprises a diallyl phenyl compound and a thermoplastic resin.
8. The modified bismaleimide resin composition of claim 7 wherein the diallyl phenyl compound comprises at least one of diallyl bisphenol a, bisphenol a bis-diallyl ether, or diallyl bisphenol S.
9. The modified bismaleimide resin composition of claim 7 wherein the modified bismaleimide resin composition is a mixture and the process of forming the mixture comprises:
sequentially adding the bismaleimide, the thermoplastic resin and the toughening modifier into a diallyl phenyl compound to be mixed to obtain the mixture.
10. The modified bismaleimide resin composition according to claim 7, wherein the bismaleimide resin composition comprises, in mass percent: 10% -25% of diallyl phenyl compound, 35% -50% of bismaleimide, 5% -25% of thermoplastic resin and 5% -20% of toughening modifier.
11. The modified bismaleimide resin composition according to claim 7, wherein the bismaleimide resin composition comprises, in mass percent: 15-25% of diallyl phenyl compound, 40-50% of bismaleimide, 10-20% of thermoplastic resin and 5-15% of toughening modifier.
12. The modified bismaleimide resin composition of claim 7, wherein the thermoplastic resin comprises at least one of polyimide, polyethersulfone or polyetherimide.
13. The modified bismaleimide resin composition according to claim 7 wherein the bismaleimide comprises at least one of N, N- (4, 4-methylenediphenyl) bismaleimide or N, N- (4-methyl-1, 3-phenylene) bismaleimide, N- (1, 4-phenylene) bismaleimide.
14. The modified bismaleimide resin composition of claim 9 wherein the process of forming the mixture comprises: preheating the diallyl phenyl compound at 85-90 ℃ for 25-40min, and then sequentially adding the bismaleimide, the thermoplastic resin and the toughening modifier.
15. A modified bismaleimide resin cured product obtained by curing the modified bismaleimide resin composition according to any one of claims 6 to 14.
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| JP2000095940A (en) * | 1998-09-22 | 2000-04-04 | Dekusutaa Kk | Preparation of addition type polyimide composite material |
| CN103342892A (en) * | 2013-06-06 | 2013-10-09 | 西安交通大学 | Bimaleimide resin toughening modifiers and preparation method thereof |
| CN107022063A (en) * | 2017-04-12 | 2017-08-08 | 武汉理工大学 | A kind of antiflaming epoxy resin curing agent and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000095940A (en) * | 1998-09-22 | 2000-04-04 | Dekusutaa Kk | Preparation of addition type polyimide composite material |
| CN103342892A (en) * | 2013-06-06 | 2013-10-09 | 西安交通大学 | Bimaleimide resin toughening modifiers and preparation method thereof |
| CN107022063A (en) * | 2017-04-12 | 2017-08-08 | 武汉理工大学 | A kind of antiflaming epoxy resin curing agent and preparation method thereof |
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