CN114213631A - 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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- CN114213631A CN114213631A CN202111555082.2A CN202111555082A CN114213631A CN 114213631 A CN114213631 A CN 114213631A CN 202111555082 A CN202111555082 A CN 202111555082A CN 114213631 A CN114213631 A CN 114213631A
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- bismaleimide
- toughening
- toughening modifier
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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 205
- 229920005989 resin Polymers 0.000 title claims abstract description 161
- 239000011347 resin Substances 0.000 title claims abstract description 161
- 239000003607 modifier Substances 0.000 title claims abstract description 92
- 239000011342 resin composition Substances 0.000 title claims abstract description 55
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 81
- 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 27
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 19
- 238000007259 addition reaction Methods 0.000 claims abstract description 17
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 43
- 229920005992 thermoplastic resin Polymers 0.000 claims description 26
- -1 diallyl phenyl compound Chemical class 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 14
- 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
- 150000001875 compounds Chemical class 0.000 claims description 4
- 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
- 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 2
- 238000004132 cross linking Methods 0.000 abstract description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 70
- 238000003756 stirring Methods 0.000 description 34
- 238000001816 cooling Methods 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000012153 distilled water Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 230000008025 crystallization Effects 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
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 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
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005266 casting Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 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
- 239000000463 material 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
- 239000007787 solid 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (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 flexible group is introduced by utilizing the ring-opening reaction of active hydrogen on the amino group of the addition product and an epoxy group in the bisphenol A diglycidyl ether. The toughening composition can reduce the crosslinking density of a bismaleimide resin cured product, the flexible chain can rotate, the toughness of the resin is enhanced, the mechanical property of the resin can be improved, and the application performance and the application range can be enlarged.
Description
Technical Field
The invention relates to the technical field of bismaleimide resin, and particularly relates 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 moisture and heat resistance, electrical insulation performance, flame retardant performance, radiation resistance and mechanical property, and becomes a main competitor in the field of thermosetting materials. However, due to the rigid structure and the large crosslinking density of the bismaleimide resin, and the existence of the polar carbonyl group, polymer chains are orderly stacked, so that the energy dissipation probability is reduced, the toughness of the bismaleimide resin is poor, and the use performance and the use range of the bismaleimide resin are reduced to a certain extent.
In view of the above, the present invention is particularly proposed.
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 service performance and the use 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 including, 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 comprises the following components in percentage by mass: 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 by using the above resin toughening composition.
Further, the preparation method of the resin toughening modifier comprises the following steps: step S1, carrying out addition reaction on diphenylmethane bismaleimide and diaminodiphenylmethane to obtain an addition product system; and step S2, carrying out ring-opening reaction on the addition product in the addition product system and bisphenol A diglycidyl ether to obtain the resin toughening modifier.
Further, step S1 includes: A. dissolving diphenylmethane bismaleimide and diaminodiphenylmethane in a solvent respectively to obtain a diphenylmethane bismaleimide solution and a diaminodiphenylmethane solution; B. mixing a diphenylmethane bismaleimide solution and a 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 25-40 min; preferably, the solvent in which the diphenylmethane bismaleimide and the diaminodiphenylmethane are dissolved each independently comprises 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 40-50 min; further, before the ring-opening reaction is carried out, it is preferable that step S2 further includes preheating bisphenol A glycidyl ether at 80-90 deg.C for 25-40 min.
According to a third aspect of the present invention, there is provided a modified bismaleimide resin composition comprising bismaleimide and a toughening modifier, the toughening modifier being the resin toughening modifier provided in the second aspect above.
Further, the modified bismaleimide resin composition further comprises a diallylphenyl compound and a thermoplastic resin. Further, the bismaleimide resin composition comprises, by 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 comprises, by 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 includes 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, N- (4-methyl-1, 3 phenylene) bismaleimide, and N, N- (1,4 phenylene) bismaleimide.
Further, the bismaleimide resin composition is a mixture, and the process of forming the mixture comprises: adding bismaleimide, thermoplastic resin and toughening modifier into a diallyl phenyl compound in sequence, and mixing to obtain a mixture; preferably, the diallyl phenyl compound is preheated at 85-90 ℃ for 25-40min, and then the bismaleimide, the thermoplastic resin and the toughening modifier are sequentially added.
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 of the third aspect.
By applying the technical scheme of the invention, the invention at least has the following beneficial effects:
according to the bismaleimide resin toughening modifier provided by the invention, the molecular chain of diphenylmethane bismaleimide is expanded by utilizing the addition reaction of diphenylmethane bismaleimide and diaminodiphenylmethane, and then the active hydrogen on the amino group of the addition product and the epoxy group in bisphenol A diglycidyl ether are subjected to a ring-opening reaction to introduce a flexible group. Therefore, after the modified bismaleimide resin is used as a toughening modifier and added into a bismaleimide resin system, the crosslinking density of a bismaleimide resin cured product can be reduced, the 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 expanded.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As analyzed by the background technology of the application, due to the rigid structure and the large crosslinking density of the bismaleimide resin and the existence of the polar carbonyl group, polymer chains are orderly stacked, the energy dissipation probability is reduced, the toughness of the bismaleimide resin is poor, and the use performance and the use range of the bismaleimide resin are reduced to a certain extent. In order to solve the problem, the 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 including, 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 a diepoxy functional group, and is favorable for ring-opening reaction with other substances.
According to the resin toughening composition, the diphenylmethane bismaleimide can perform addition reaction with diaminodiphenylmethane to expand a molecular chain, active hydrogen on an amino group of an addition product can perform 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 a bismaleimide resin system, the crosslinking density of a bismaleimide resin cured product can be reduced, external energy can be absorbed by utilizing the rotation of a flexible chain, the toughness of the resin cured product is enhanced, the mechanical property is improved, and the service performance and the use range of the bismaleimide resin are favorably expanded.
Typically, but not by way of limitation, the amount of diphenylmethane bismaleimide present in the resin toughening composition, by weight percent, is, for example, 30%, 35%, 40%, 45%, 50%, or 55%; the content of diaminodiphenylmethane 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 the diphenylmethane bismaleimide is 45% to 50%, the content of the diaminodiphenylmethane is 20% to 25%, and the content of the bisphenol a diglycidyl ether is 25% to 30% by mass, 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 prepared from the above resin toughening composition is provided.
The application provides a resin toughening modifier, through diaminodiphenylmethane extension diphenylmethane bismaleimide molecular chain, introduce flexible group through bisphenol A diglycidyl ether, make it add bismaleimide resin system after, not only can reduce the crosslink density of cured object, can improve toughness and the mechanical strength of cured object moreover.
In some embodiments of the present application, a method of preparing a resin toughening modifier includes: step S1, carrying out addition reaction on diphenylmethane bismaleimide and diaminodiphenylmethane to obtain an addition product system; and step S2, carrying out ring-opening reaction on the addition product in the addition product system and bisphenol A diglycidyl ether to obtain the resin toughening modifier.
In the step S1, diaminodiphenylmethane and diphenylmethane bismaleimide undergo an addition reaction, and an amino group with active hydrogen is introduced into the addition product while the molecular chain of diphenylmethane bismaleimide is expanded, so that the subsequent reaction of the active hydrogen on the amino group with a substance containing a flexible chain is facilitated, and a flexible group is introduced.
In some preferred embodiments of the present application, step S1 includes: A. dissolving diphenylmethane bismaleimide and diaminodiphenylmethane in a solvent respectively 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. The diphenylmethane bismaleimide and the diaminodiphenylmethane are respectively dissolved 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 step a, the solvents for dissolving the diphenylmethane bismaleimide and the diaminodiphenylmethane may be the same or different, as long as the diphenylmethane bismaleimide or the diaminodiphenylmethane can be dissolved.
Preferably, the solvent for dissolving the diphenylmethane bismaleimide and the diaminodiphenylmethane is independently any one or more of N, N-dimethylacetamide, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, acetonitrile or N-methylpyrrolidone.
In some embodiments, in the step B, the temperature of the addition reaction is 80-90 ℃ and the time is 25-40min, which is beneficial to the more sufficient progress of the addition reaction and improves the efficiency of the addition reaction.
Typically, but not by way of limitation, the addition reaction is carried out at a temperature such as 80 deg.C, 82 deg.C, 85 deg.C, 88 deg.C or 90 deg.C for a period of time such as 25min, 28min, 30min, 32min, 35min, 38min or 40 min.
After the addition product system is obtained, the addition product system and the bisphenol A diglycidyl ether can be directly utilized for the next ring-opening reaction. 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, the step B further comprises mixing the addition product system with water, crystallizing, separating solid from liquid, and drying to obtain the addition product.
The crystallization method includes, but is not limited to, the following methods: adding the addition product system into distilled water, and cooling and crystallizing at 20-30 ℃.
Preferably, the water includes, but is not limited to, distilled, deionized 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 group of the addition product and the epoxy group in the diglycidyl ether of bisphenol a are subjected to a ring-opening reaction, so that a flexible group is introduced into the resin toughening modifier, and the toughness and the mechanical property of the bismaleimide resin can be effectively enhanced after the resin toughening modifier 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 to 100 ℃ and the time is 40 to 50min, the ring-opening reaction is more favorably performed more sufficiently, and the efficiency of the ring-opening reaction is improved.
Typically, but not by way of limitation, the ring-opening reaction is carried out at a temperature of, e.g., 90 deg.C, 92 deg.C, 95 deg.C, 98 deg.C or 100 deg.C for a period of, e.g., 40min, 42min, 45min, 48min or 50 min.
Preferably, in step S2, before the ring-opening reaction, preheating bisphenol A glycidyl ether at 80-90 ℃ for 25-40min is further included, 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, e.g., 80 deg.C, 82 deg.C, 85 deg.C, 88 deg.C or 90 deg.C for a time of, e.g., 25min, 28min, 30min, 32min, 35min or 40 min.
In a third exemplary embodiment of the present application, there is provided a modified bismaleimide resin composition comprising bismaleimide and a toughening modifier, the toughening modifier being the resin toughening modifier provided in the second exemplary embodiment described above.
In the bismaleimide resin composition provided by the application, the resin toughening modifier is introduced into the bismaleimide resin, so that on the basis of ensuring the humidity resistance of the bismaleimide resin, the crosslinking density of a bismaleimide resin cured product can be reduced, the toughness and the mechanical performance can be enhanced, and the service performance and the use range of the bismaleimide resin can be favorably expanded.
Preferably, the bismaleimide includes but is not limited to N, N- (4, 4-methylene diphenyl) 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 comprises a diallylbenzene compound and a thermoplastic resin.
The allyl compound is added into the modified bismaleimide resin composition for copolymerization modification, which is beneficial to improving the heat resistance and mechanical property of the bismaleimide resin condensate. The thermoplastic resin generally has outstanding toughness, molecular chains are in a linear structure and can be softened and flow by heating and pressurizing, 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, the further development of cracks is effectively prevented, meanwhile, the bismaleimide resin can be toughened by cooperating with a 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 diallyl phenyl compound and the thermoplastic resin can adopt corresponding substances commonly used in the modification of bismaleimide resin, 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
The thermoplastic resin includes but is not limited to any one or a mixture of polyimide, polyether sulfone or polyether imide.
In some preferred embodiments of the present application, 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.
By adopting the mutual matching of the diallyl phenyl compound, the bismaleimide, the thermoplastic resin and the toughening modifier in a specific mass ratio, the prepared maleimide resin can obviously improve the toughness and the mechanical strength on the basis of ensuring the heat resistance, thereby being beneficial to expanding the service performance and the application range of the bismaleimide resin.
Typically, but not limitatively, 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 the 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%, in percentage by mass.
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 in percentage by mass, the raw materials are cooperated with each other, and the prepared bismaleimide resin is more excellent in heat resistance, toughness and mechanical properties.
The components in the modified bismaleimide resin composition can be packaged independently and then sold in combination, and because the components can exist relatively stably at room temperature, the modified bismaleimide resin composition can also be a mixture, and the process of forming the mixture comprises the following steps: and sequentially adding bismaleimide, thermoplastic resin and toughening modifier into the diallyl phenyl compound for mixing to obtain the mixture.
Preferably, the diallyl phenyl compound is preheated for 25-40min at 85-90 ℃, and then the bismaleimide, the thermoplastic resin and the toughening modifier are sequentially added, so that the raw materials are mixed more uniformly.
Typically, but not by way of limitation, the diallyl phenyl compound is preheated at a temperature of, e.g., 85 deg.C, 86 deg.C, 87 deg.C, 88 deg.C, 89 deg.C or 90 deg.C for a time of, e.g., 25min, 28min, 30min, 32min, 35min, 38min or 40 min.
In a fourth exemplary embodiment of the present application, a bismaleimide resin cured product is provided, which is obtained by curing the modified bismaleimide resin composition provided in the third exemplary embodiment of the present application.
In the bismaleimide resin condensate provided by the application, the toughening modifier is introduced, so that the crosslinking density of the condensate is reduced, and the flexible chain in the toughening modifier is used for absorbing external energy and enhancing the toughness; the introduction of the allyl compound is beneficial to improving the heat resistance and the mechanical property of a 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 further development of cracks.
The bismaleimide resin condensate provided by the application is characterized in that the diallyl phenyl compound, the bismaleimide, the thermoplastic resin and the toughening modifier are matched with each other, so that the toughness and the mechanical strength are obviously improved on the basis of reducing the crosslinking density and ensuring the heat resistance, and the use performance and the use range of the bismaleimide resin are favorably expanded.
In some embodiments of the present application, a method for preparing a modified bismaleimide resin cured product includes: and vacuumizing the modified bismaleimide resin composition to remove air bubbles, and pouring and curing to obtain a modified bismaleimide resin cured product.
Preferably, the curing process of casting and curing comprises four stages, wherein the first stage is at 155 ℃ of 145-.
In an exemplary embodiment of the present application, the curing process is performed as follows: the first stage is kept at 150 ℃ for 1h, then the temperature is raised to the second stage and kept at 180 ℃ for 1h, then the temperature is raised to the third stage and kept at 200 ℃ for 1h, finally the temperature is raised to the fourth stage and kept at 230 ℃ for 2h, and the modified bismaleimide resin condensate is obtained after cooling.
The cooling method 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 with reference to examples and comparative examples.
Example 1
The embodiment provides a resin toughening modifier, which is prepared according to the following steps:
(1) 30g of diphenylmethane bismaleimide is dissolved in 200mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. 30g of diaminodiphenylmethane was dissolved in 250ml of N, N-dimethylacetamide, and the mixture was stirred uniformly to dissolve diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the two solutions, stirring at 80-90 deg.C for reaction for 30min, pouring the above solution into distilled water after reaction, cooling at 20-30 deg.C for crystallization, filtering, and drying to obtain addition product.
(2) Heating 40g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react 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 according to the following steps:
(1) dissolving 55g of diphenylmethane bismaleimide in 400mL of N, N-dimethylacetamide, and uniformly stirring to completely dissolve the diphenylmethane bismaleimide in the N, N-dimethylacetamide. Dissolving 15g of diaminodiphenylmethane in 130ml of N-dimethylacetamide, and uniformly stirring to completely dissolve the diaminodiphenylmethane in the N, N-dimethylacetamide. Mixing the two solutions, stirring at 80-90 deg.C for reaction for 30min, pouring the above solution into distilled water after reaction, cooling at 20-30 deg.C for crystallization, filtering, and drying to obtain addition product.
(2) Heating 30g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react 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 according to the following steps:
(1) 50g of diphenylmethane bismaleimide is dissolved in 400mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. 30g of diaminodiphenylmethane was dissolved in 250ml of N, N-dimethylacetamide, and the mixture was stirred uniformly to dissolve diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the two solutions, stirring at 80-90 deg.C for reaction for 30min, pouring the above solution into distilled water after reaction, cooling at 20-30 deg.C for crystallization, filtering, and drying to obtain addition product.
(2) Heating 20g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react 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 according to the following steps:
(1) 45g of diphenylmethane bismaleimide is dissolved in 300mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. 25g of diaminodiphenylmethane was dissolved in 250ml of N, N-dimethylacetamide, and stirred uniformly to dissolve diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the two solutions, stirring at 80-90 deg.C for reaction for 30min, pouring the above solution into distilled water after reaction, cooling at 20-30 deg.C for crystallization, filtering, and drying to obtain addition product.
(2) Heating 30g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react 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 according to the following steps:
(1) 50g of diphenylmethane bismaleimide is dissolved in 400mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. 25g of diaminodiphenylmethane was dissolved in 250ml of N, N-dimethylacetamide, and stirred uniformly to dissolve diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the two solutions, stirring at 80-90 deg.C for reaction for 30min, pouring the above solution into distilled water after reaction, cooling at 20-30 deg.C for crystallization, filtering, and drying to obtain addition product.
(2) Heating 25g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react 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 according to the following steps:
(1) 50g of diphenylmethane bismaleimide is dissolved in 400mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. Dissolving 20g of diaminodiphenylmethane in 200ml of N, N-dimethylacetamide, and uniformly stirring to completely dissolve the diaminodiphenylmethane in the N, N-dimethylacetamide. Mixing the two solutions, stirring at 80-90 deg.C for reaction for 30min, pouring the above solution into distilled water after reaction, cooling at 20-30 deg.C for crystallization, filtering, and drying to obtain addition product.
(2) Heating 30g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react 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 according to the following steps:
(1) 48g of diphenylmethane bismaleimide is dissolved in 350mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. 24g of diaminodiphenylmethane was dissolved in 250ml of N, N-dimethylacetamide, and stirred uniformly to dissolve the diaminodiphenylmethane completely in the N, N-dimethylacetamide. Mixing the two solutions, stirring at 80-90 deg.C for reaction for 30min, pouring the above solution into distilled water after reaction, cooling at 20-30 deg.C for crystallization, filtering, and drying to obtain addition product.
(2) Heating 28g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Comparative example 1
This comparative example provides a resin toughening modifier, which is different from example 7 in that hexamethylenediamine is used in place of diaminodiphenylmethane in step (1), and the rest of the raw materials and the preparation method are the same as those in example 7, and are not described again.
Comparative example 2
This comparative example provides a resin toughening modifier, which is different from example 7 in that, in step (2), diglycidyl ether of adipic acid is used instead of diglycidyl ether of bisphenol a, and the rest of the raw materials and the preparation method are the same as those in example 7, and are not described again.
Comparative example 3
The comparative example provides a resin toughening modifier, which is prepared according to the following steps:
(1) 48g of diphenylmethane bismaleimide is dissolved in 350mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. 5g of diaminodiphenylmethane was dissolved in 50ml of N, N-dimethylacetamide, and the mixture was stirred uniformly to dissolve diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the two solutions, stirring and reacting at 80-90 ℃ for 30min, pouring the solution into distilled water after the reaction is finished, crystallizing, filtering and drying to obtain an addition product.
(2) Heating 47g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react 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 according to the following steps:
(1) 48g of diphenylmethane bismaleimide is dissolved in 350mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. 40g of diaminodiphenylmethane was dissolved in 400ml of N, N-dimethylacetamide, and stirred uniformly to dissolve diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the two solutions, stirring and reacting at 80-90 ℃ for 30min, pouring the solution into distilled water after the reaction is finished, crystallizing, filtering and drying to obtain an addition product.
(2) Heating 12g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react 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 according to the following steps:
(1) 20g of diphenylmethane bismaleimide is dissolved in 150mL of N, N-dimethylacetamide, and the mixture is stirred uniformly to ensure that the diphenylmethane bismaleimide is completely dissolved in the N, N-dimethylacetamide. 40g of diaminodiphenylmethane was dissolved in 400ml of N, N-dimethylacetamide, and stirred uniformly to dissolve diaminodiphenylmethane completely in N, N-dimethylacetamide. Mixing the two solutions, stirring and reacting at 80-90 ℃ for 30min, pouring the solution into distilled water after the reaction is finished, crystallizing, filtering and drying to obtain an addition product.
(2) Heating 30g of bisphenol A diglycidyl ether at 80-90 ℃ for 30min, adding the addition product, heating to react at 90-100 ℃ for 40-50min, and cooling to obtain the resin toughening modifier.
Example 8
The embodiment provides a modified bismaleimide resin cured product, which is prepared according to the following steps:
(1) adding 50g of diallyl bisphenol A into a three-neck flask, heating to 90 ℃, adding 100g N N- (1, 4-phenylene) bismaleimide under the stirring state, stirring and dissolving to form a homogeneous phase, adding 32g of polyether sulfone and 18g of the resin toughening modifier provided in the embodiment 1, and uniformly stirring to obtain a modified bismaleimide resin composition;
(2) vacuumizing the modified bismaleimide resin composition to remove bubbles, and curing the cast bismaleimide resin composition according to the following process: the first stage is kept at 150 ℃ for 1h, then the temperature is raised to the second stage and kept at 180 ℃ for 1h, then the temperature is raised to the third stage and kept at 200 ℃ for 1h, finally the temperature is raised to the fourth stage and kept at 230 ℃ for 2h, and the modified bismaleimide resin condensate is obtained after cooling.
Examples 9 to 14
Examples 9 to 14 each provide a modified bismaleimide resin cured product which is different from example 8 in that the resin toughening modifiers provided in examples 2 to 7 are used instead of the resin toughening modifier provided in example 1.
Example 15
The embodiment provides a modified bismaleimide resin cured product, 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 N N- (4, 4-methylene diphenyl) bismaleimide under the stirring state, stirring and dissolving to form a homogeneous phase, adding 36g of polyimide and 21g of the resin toughening modifier provided in the embodiment 7, and stirring uniformly to obtain a modified bismaleimide resin composition;
(2) vacuumizing the modified bismaleimide resin composition to remove bubbles, and curing the cast bismaleimide resin composition according to the following process: the first stage is kept at 150 ℃ for 1h, then the temperature is raised to the second stage and kept at 180 ℃ for 1h, then the temperature is raised to the third stage and kept at 200 ℃ for 1h, finally the temperature is raised to the fourth stage and kept at 230 ℃ for 2h, and the modified bismaleimide resin condensate is obtained after cooling.
Example 16
The embodiment provides a modified bismaleimide resin cured product, 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 N N- (1, 4-phenylene) bismaleimide under the stirring state, stirring and dissolving to form a homogeneous phase, adding 41g of polyimide and 18g of the resin toughening modifier provided in the embodiment 7, and uniformly stirring to obtain a modified bismaleimide resin composition;
(2) vacuumizing the modified bismaleimide resin composition to remove bubbles, and curing the cast bismaleimide resin composition according to the following process: the first stage is kept at 150 ℃ for 1h, then the temperature is raised to the second stage and kept at 180 ℃ for 1h, then the temperature is raised to the third stage and kept at 200 ℃ for 1h, finally the temperature is raised to the fourth stage and kept at 230 ℃ for 2h, and the modified bismaleimide resin condensate is obtained after cooling.
Example 17
The embodiment provides a modified bismaleimide resin cured product, which is prepared according to the following steps:
(1) adding 50g of diallyl bisphenol A into a three-neck flask, heating to 90 ℃, adding 100g N N- (1, 4-phenylene) bismaleimide under the stirring state, stirring and dissolving to form a homogeneous phase, adding 10g of polyether sulfone and 40g of the resin toughening modifier provided in the embodiment 1, and uniformly stirring to obtain a modified bismaleimide resin composition;
(2) vacuumizing the modified bismaleimide resin composition to remove bubbles, and curing the cast bismaleimide resin composition according to the following process: the first stage is kept at 150 ℃ for 1h, then the temperature is raised to the second stage and kept at 180 ℃ for 1h, then the temperature is raised to the third stage and kept at 200 ℃ for 1h, finally the temperature is raised to the fourth stage and kept at 230 ℃ for 2h, and the modified bismaleimide resin condensate is obtained after cooling.
Example 18
The embodiment provides a modified bismaleimide resin cured product, 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 N N- (1, 4-phenylene) bismaleimide under the stirring state, stirring and dissolving to form a homogeneous phase, adding 50g of polyether sulfone and 30g of the resin toughening modifier provided in the embodiment 1, and uniformly stirring to obtain a modified bismaleimide resin composition;
(2) vacuumizing the modified bismaleimide resin composition to remove bubbles, and curing the cast bismaleimide resin composition according to the following process: the first stage is kept at 150 ℃ for 1h, then the temperature is raised to the second stage and kept at 180 ℃ for 1h, then the temperature is raised to the third stage and kept at 200 ℃ for 1h, finally the temperature is raised to the fourth stage and kept at 230 ℃ for 2h, and the modified bismaleimide resin condensate is obtained after cooling.
Example 19
The embodiment provides a modified bismaleimide resin cured product, which is prepared according to the following steps:
(1) adding 50g of diallyl bisphenol A into a three-neck flask, heating to 90 ℃, adding 80g N N- (1, 4-phenylene) bismaleimide under the stirring state, stirring and dissolving to form a homogeneous phase, adding 40g of polyether sulfone and 30g of the resin toughening modifier provided in the embodiment 1, and uniformly stirring to obtain a modified bismaleimide resin composition;
(2) vacuumizing the modified bismaleimide resin composition to remove bubbles, and curing the cast bismaleimide resin composition according to the following process: the first stage is kept at 150 ℃ for 1h, then the temperature is raised to the second stage and kept at 180 ℃ for 1h, then the temperature is raised to the third stage and kept at 200 ℃ for 1h, finally the temperature is raised to the fourth stage and kept at 230 ℃ for 2h, and the modified bismaleimide resin condensate is obtained after cooling.
Example 20
The embodiment provides a modified bismaleimide resin cured product, 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 N N- (1, 4-phenylene) bismaleimide under the stirring state, stirring and dissolving to form a homogeneous phase, adding 40g of polyether sulfone and 30g of the resin toughening modifier provided in the embodiment 1, and uniformly stirring to obtain a modified bismaleimide resin composition;
(2) vacuumizing the modified bismaleimide resin composition to remove bubbles, and curing the cast bismaleimide resin composition according to the following process: the first stage is kept at 150 ℃ for 1h, then the temperature is raised to the second stage and kept at 180 ℃ for 1h, then the temperature is raised to the third stage and kept at 200 ℃ for 1h, finally the temperature is raised to the fourth stage and kept at 230 ℃ for 2h, and the modified bismaleimide resin condensate is obtained after cooling.
Example 21
This comparative example provides a modified bismaleimide resin cured product, which is different 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 polyether sulfone is 40g, the amount of a resin toughening modifier is 50g, and the remaining steps are the same as example 14 and are not described again.
Example 22
This comparative example provides a modified bismaleimide resin cured product, which is different 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 polyether sulfone is 60g, the amount of a resin toughening modifier is 5g, and the remaining steps are the same as example 14 and are not described again.
Example 23
This example provides a modified bismaleimide resin cured product, which is different from example 14 in that polyethersulfone is not added in the process of preparing the modified bismaleimide resin composition in step (1), and the remaining raw materials and the preparation method are the same as those in example 14, and are not described herein again.
Example 24
This example provides a modified bismaleimide resin cured product, which is different from example 14 in that diallyl bisphenol a is not added in the process of preparing the modified bismaleimide resin composition in step (1), and the remaining raw materials and the preparation method are the same as those in example 14, and are not described herein again.
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 the impact strength test and the flexural strength test, and the results are shown in table 1 below, wherein the impact strength was measured according to the test standard GB/T2567-2008, and the flexural strength was measured according to the test standard astm d 7264.
Table 1 Table for strength data of cured products of modified bismaleimide resins provided in examples and comparative examples
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
according to the maleimide resin cured product, the resin toughening modifier formed by copolymerizing diphenylmethane bismaleimide, diaminodiphenylmethane and bisphenol A diglycidyl ether is introduced into a bismaleimide resin system, and through mutual matching of the diallyl phenyl compound, bismaleimide, thermoplastic resin and the toughening modifier, on the basis of reducing the crosslinking density and ensuring the heat resistance, the toughness and the mechanical strength are remarkably improved, and the use performance and the use range of the bismaleimide resin are favorably expanded.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A resin toughening composition, characterized in that, by mass percent, the resin toughening composition comprises: 30-55% of diphenylmethane bismaleimide, 15-30% of diaminodiphenylmethane and 20-40% of bisphenol A diglycidyl ether.
2. The resin toughening composition 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. A resin toughening modifier, characterized in that the resin toughening modifier is prepared by using the resin toughening composition of claim 1 or 2.
4. The resin toughening modifier of claim 3, wherein the preparation method of the resin toughening modifier comprises:
step S1, performing addition reaction on the diphenylmethane bismaleimide and the diaminodiphenylmethane to obtain an addition product system;
and step S2, carrying out ring-opening reaction on the addition product in the addition product system and the bisphenol A diglycidyl ether to obtain the resin toughening modifier.
5. The resin toughening modifier of claim 4, wherein the step S1 includes:
A. respectively dissolving the diphenylmethane bismaleimide and the diaminodiphenylmethane in a solvent to obtain a diphenylmethane bismaleimide solution and a diaminodiphenylmethane solution;
B. mixing the diphenylmethane bismaleimide solution and the diaminodiphenylmethane solution for the addition reaction to obtain an addition product system, wherein the temperature of the addition reaction is preferably 80-90 ℃ and the time is preferably 25-40 min;
preferably, the solvent in which the diphenylmethane bismaleimide and the diaminodiphenylmethane are dissolved each independently comprises at least one of N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide, tetrahydrofuran, acetonitrile, or N-methylpyrrolidone.
6. The resin toughening modifier according to claim 4, wherein the temperature of the ring-opening reaction is 90-100 ℃ and the time is 40-50 min;
preferably, the step S2 further comprises preheating the bisphenol A diglycidyl ether at 80-90 ℃ for 25-40min before performing the ring-opening reaction.
7. A modified bismaleimide resin composition comprising bismaleimide and a toughening modifier, wherein the toughening modifier is the resin toughening modifier of any one of claims 3 to 6.
8. The modified bismaleimide resin composition of claim 7 wherein the modified bismaleimide resin composition further comprises a diallylphenyl compound and a thermoplastic resin;
preferably, the bismaleimide resin composition comprises, in mass percent: 10% -25% of the diallyl phenyl compound, 35% -50% of the bismaleimide, 5% -25% of the thermoplastic resin and 5% -20% of the toughening modifier;
preferably, the bismaleimide resin composition comprises, in mass percent: 15% -25% of the diallyl phenyl compound, 40% -50% of the bismaleimide, 10% -20% of the thermoplastic resin and 5% -15% of the toughening modifier.
9. The modified bismaleimide resin composition of claim 8 wherein the diallylphenyl compound comprises at least one of diallylbisphenol a, bisphenol a bisdiallylether, or diallylbisphenol S;
preferably, the thermoplastic resin comprises at least one of polyimide, polyethersulfone, or polyetherimide;
preferably, 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.
10. The modified bismaleimide resin composition of claim 8 wherein the modified bismaleimide resin composition is a mixture formed by a process comprising:
sequentially adding bismaleimide, thermoplastic resin and a toughening modifier into a diallyl phenyl compound to be mixed to obtain a mixture;
preferably, the diallyl phenyl compound is preheated at 85-90 ℃ for 25-40min, and then the bismaleimide, the thermoplastic resin and the toughening modifier are sequentially added.
11. A modified bismaleimide resin cured product obtained by curing the modified bismaleimide resin composition according to any one of claims 7 to 9.
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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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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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