CN107011657A - A kind of high-ductility bimaleimide resin and its preparation method and application - Google Patents
A kind of high-ductility bimaleimide resin and its preparation method and application Download PDFInfo
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- CN107011657A CN107011657A CN201710193074.5A CN201710193074A CN107011657A CN 107011657 A CN107011657 A CN 107011657A CN 201710193074 A CN201710193074 A CN 201710193074A CN 107011657 A CN107011657 A CN 107011657A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08L79/085—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention belongs to technical field of polymer materials, and in particular to high-ductility bimaleimide resin, BMI solidified resin, preparation method, the prepreg containing the resin and the composite prepared by the prepreg of two kinds of resins.Bismaleimide resin prepared by the present invention is a kind of high performance resin for integrating heat resistance, mechanical property and processing characteristics, and its heat decomposition temperature is all higher than 440 DEG C, while solidfied material impact strength is all higher than 20KJ/m2, wherein maximum 30KJ/m2, it is on close level with epoxy resin.The composite CAI values for using bismaleimide resin to be prepared for matrix may be up to 240MPa, meet aerospace structure part use requirement.
Description
Technical field
The invention belongs to technical field of polymer materials, and in particular to high-ductility bimaleimide resin, bismaleimide
Preparation method, the prepreg containing the resin and the composite wood prepared by the prepreg of amine solidified resin, two kinds of resins
Material.
Background technology
Bimaleimide resin (referred to as " bismaleimide resin ") is with its excellent heat resistance, radiation hardness, wet-heat resisting, mechanical property
The features such as energy, has a wide range of applications in fields such as Aeronautics and Astronautics, machinery, electronics.But the crosslink density of bismaleimide resin is too high,
Molecule chain rigidity is big, causes its poor toughness, it is impossible to meet toughness reguirements of the advanced configuration composite to resin matrix.Therefore carry
The toughness of high span is always one of direction that researcher makes great efforts.
The method of current bismaleimide resin toughening modifying mainly has following several：Diamine is modified, modified rubber, epoxy resin
Modified, allyl compound is modified, and interior chain extension is modified, thermoplasticity big molecular modification, nanometer particle-modified etc..
Although larger using diamine, rubber, epoxy resin modification toughness increase rate, under the heat resistance of resin
Drop is obvious.Allyl compound is that, using most ripe toughening modifying method, although modified bismaleimide resin toughness carried
Height, but modified span softening point is higher, is not suitable for dry process prepreg.Needed using interior chain extension toughening modifying to molecule
Structure redesigns synthesis, needs longer time from mass steady production is synthesized to, research cost is high.It is big using thermoplasticity
Molecule or nano-particle toughening, which are modified, can largely improve the toughness of span, but the viscosity of resin can be increased substantially,
Cause the poor processability of resin.
Suitable for dry method prepeg process high-ductility bismaleimide resin in addition to toughness reguirements, while also requiring bismaleimide resin
Softening point is low, and room temperature has being coated with property；High temperature viscosity is more than 3Pa.s, and the bismaleimide resin glued membrane being prepared could be complete, molding
When gummosis it is not serious, the size of composite is easily controllable.Current toughness reinforcing bismaleimide resin suitable dry method prepreg difficult to realize
Technique.
The content of the invention
It is an object of the invention to improve above-mentioned the deficiencies in the prior art there is provided a kind of high-ductility bimaleimide resin,
BMI solidified resin, the preparation method of two kinds of resins, the prepreg containing the resin and prepared by the prepreg
Composite.
The first aspect of the present invention is to provide a kind of bismaleimide amine composition for preparing bimaleimide resin, institute
Stating composition includes the component of following parts by weight：
20-100 parts of bismaleimide monomer,
10-90 parts of allyl compound,
5-25 parts of thermoplasticity macromolecular,
3-10 parts of polyfunctional epoxy resin；
Wherein, the bismaleimide monomer, allyl compound, the parts by weight sum of thermoplasticity macromolecular are 100
Part；The parts by weight of polyfunctional epoxy resin are relative to bismaleimide monomer, allyl compound and thermoplasticity macromolecular
Parts by weight sum for.
According to the present invention, the composition also includes 0.1-10 parts of surface modifier, and the parts by weight of surface modifier are
For the parts by weight sum of bismaleimide monomer, allyl compound and thermoplasticity macromolecular.
According to the present invention, the composition still further comprises 0.1-2 parts of free radical scavenger, free radical scavenger
Parts by weight are for the parts by weight sum of bismaleimide monomer, allyl compound and thermoplasticity macromolecular.
According to the present invention, the bismaleimide monomer is selected from N, N ' -4,4 ' diphenyl methane dimaleimides, 2- first
Base -1,5- dimaleoyl iminos benzene, 2,2 '-bis- [4- (4- maleimide phenoxyls) phenyl] propane or 3- allyloxys
One or more in single maleimide.
Preferably, the bismaleimide monomer is the combination of two groups of monomers, and first group of monomer is selected from N, N ' -4,4 ' two
Phenylmethane BMI, second group of monomer is selected from 2- methyl isophthalic acids, 5- dimaleoyl iminos benzene, 2,2 '-bis- [4- (4- horses
Carry out imide phenoxy group) phenyl] propane or one kind in 3- allyloxy list maleimides, two or three.
It is further preferred that the bismaleimide monomer be selected from N, N ' -4,4 ' diphenyl methane dimaleimides and
2- methyl isophthalic acids, the mixture or N, N ' -4,4 ' diphenyl methane dimaleimide and 3- allyls of 5- dimaleoyl imino benzene
The mixture or N, N ' -4,4 ' diphenyl methane dimaleimide of epoxide list maleimide, 2,2 '-bis- [4- (4- Malaysias acyls
Imines phenoxyl) phenyl] propane and 3- allyloxy list maleimides mixture.
Preferably, the parts by weight of the bismaleimide monomer are 40-60 parts.It is further preferred that when the span
Come dant monomer for two groups of monomers combination when, with the gross weight meter of bismaleimide monomer, the weight of first group of monomer
Percentage is 20-90wt%, and the percentage by weight of second group of monomer is 10-80wt%.It is further preferred that the weight of first group of monomer
Percentage is 50-80wt%, and the percentage by weight of second group of monomer is 20-50wt%.
According to the present invention, the allyl compound is selected from diallyl bisphenol, diallyl bisphenol ether, hexafluoro diene
One or more in propyl group bisphenol-A, diallyl bisphenol S or chavicol.Preferably, the weight of the allyl compound
It is 20-50 parts to measure part.
According to the present invention, the thermoplasticity macromolecular is selected from PEI (PEI), polyether sulfone (PES), polyphenylene oxide
(PPO), polyimides (PI), polyether-ether-ketone (PEEK), one kind in PAEK (PEK-C) or its a variety of combination.It is preferred that
Ground, the parts by weight of the thermoplasticity macromolecular are 5-20 parts.
According to the present invention, the polyfunctional epoxy resin is selected from 4,5- oxepane -1,2- dicarboxylic acid diglycidyl esters
(TDE-85), one in 4,4 '-MDA epoxy resin (AG80), ammonia phenolic group trifunctional epoxy resin (AFG90)
Plant or its a variety of combination.Preferably, the parts by weight of the polyfunctional epoxy resin are 3-8 parts.
According to the present invention, the surface modifier is selected from aminopropyl triethoxysilane (KH550), γ-(2,3- epoxies third
Oxygen) propyl trimethoxy silicane (KH560), vinyltrimethoxy silane (A171), polyethylene glycol (PEG, molecular weight 10000
Or one kind 20000), in ethylene oxide polymer (molecular weight 10000 or 20000 is respectively designated as P100, P200) or it is more
The combination planted.Preferably, the parts by weight of the surface modifier are 1-5 parts.
According to the present invention, the free radical scavenger is selected from 2,2,6,6- tetramethyl piperidine oxides (TEMPO), 2,6- bis-
One or more in tert-butyl-4-methyl-Phenol (BHT), 1,1- diphenylethlenes and 1,4- cyclohexadiene.Preferably, it is described
The parts by weight of free radical scavenger are 0.1-1 parts.
Allyl compound and thermoplasticity macromolecular two are with the addition of in bismaleimide amine composition of the present invention simultaneously
Component is planted, research is found, by adjusting the amount ratio of both components and bismaleimide monomer, is further preferably passed through
Select the combination of two or more bismaleimide monomer so that the BMI prepared by said composition
Resin is a kind of high performance resin for integrating heat resistance, mechanical property and processing characteristics, and its heat decomposition temperature is all higher than
440℃；The impact strength of pour mass (i.e. solidified resin) is all higher than 20KJ/m simultaneously2, wherein maximum 30KJ/m2；With relatively low
Softening point, improve toughness and suitable viscosity, be particularly suitable for use in the prepreg of dry process BMI.It is same with this
When, polyfunctional epoxy resin and optionally surface modifier have been used in bismaleimide amine composition of the present invention,
Improve the interfacial adhesion strength of resin and fiber, be conducive to improving the toughness of composite.It can be seen that, span of the present invention comes
There is synergy, not simple blending between the various components of acid imide composition；Each component is used cooperatively, obtain toughness and
Processing performance is protruded, while the high-performance bismaleimide resin that heat resistance does not decline.
The second aspect of the present invention is to provide a kind of bimaleimide resin, is led to by above-mentioned bismaleimide amine composition
Blending reaction is crossed to obtain.
The softening point of the bimaleimide resin is 40-60 DEG C, and being coated with property is good, easy film forming, high temperature (130 DEG C) viscosity
For 3-6Pas, it is adapted to prepare dry method prepreg.
The bimaleimide resin is high-ductility resin, the impact strength of the resin-cast body (i.e. solidified resin)>
20KJ/m2, the composite CAI values that the resin is prepared are more than 230MPa.
The third aspect of the present invention is to provide a kind of preparation method of bimaleimide resin as described above, including as follows
Step：By the bismaleimide monomer in the bismaleimide amine composition, allyl compound heating stirring to transparent,
Polyfunctional epoxy resin and optional ground surfactant and/or free radical scavenger are added after cooling, stirring is eventually adding thermoplastic
Property macromolecular, stirs and obtains the bimaleimide resin.
According to the present invention, in the preparation method, the temperature of the heating stirring is between 110~150 DEG C, for example
110℃。
According to the present invention, the cooling is that the temperature of reaction system is down between 80-100 DEG C, for example, be cooled to 80 DEG C.
According to the present invention, stirred after adding polyfunctional epoxy resin and optional ground surfactant and/or free radical scavenger
Mix to dissolving.
According to the present invention, it is 10-30min to add mixing time after thermoplasticity macromolecular.
The fourth aspect of the present invention is to provide a kind of BMI solidified resin, its span above-mentioned by solidifying come
Imide resin and obtain.
According to the present invention, the temperature-rise period that the solidification is used can be for：140 DEG C/2h, 180 DEG C/2h, 210 DEG C/6h.
According to the present invention, the glass transition temperature of the solidified resin is more than 250 DEG C, heat decomposition temperature>400 DEG C (preferably
More than or equal to 440 DEG C), impact strength>20KJ/m2。
The fifth aspect of the present invention is to provide a kind of preparation method of BMI solidified resin as described above, including
Following steps：
1) bimaleimide resin as described above is prepared；
2) by step 1) obtained bimaleimide resin solidified.
According to the present invention, step 1) in, prepare bimaleimide resin as described above method have as above determine
The operating procedure of justice.
According to the present invention, step 2) in, the temperature-rise period that the solidification is used has definitions as described above.
The sixth aspect of the invention is to provide a kind of prepreg, and it includes above-mentioned bimaleimide resin.
According to the present invention, reinforcing fiber is also included in the prepreg.Preferably, the reinforcing fiber can be fine for carbon
Dimension, such as T300 carbon fibers.
According to the present invention, in the prepreg, the parts by weight of bimaleimide resin are 35-40 parts；The carbon fiber
Parts by weight be 60-65 parts.
The seventh aspect of the present invention is to provide a kind of composite, and it is prepared by above-mentioned prepreg.
The beneficial effects of the invention are as follows：
1) in bismaleimide amine composition of the invention, it is modified, is further preferably made jointly using a variety of modifying agent
With the combination of two or more bismaleimide monomer so that the bimaleimide resin prepared is not only tough
Property increase rate it is larger, and resin heat resistance decline be not apparent.The resin softening point prepared simultaneously is relatively low, is adapted to
In dry process prepreg.
2) the invention discloses a kind of high-ductility bimaleimide resin.40-60 DEG C of the resin softening point, good film-forming property,
Being coated with property is good, and high temperature (130 DEG C) viscosity is 3-6Pas, it is adaptable to dry method prepeg process.The resin has high tenacity concurrently simultaneously,
Resin cured matter impact strength>20KJ/m2。
3) the invention also discloses a kind of heat resistance, mechanical property, process industrial art performance excellent bismaleimide
Amine solidified resin, its glass transition temperature is more than 250 DEG C, heat decomposition temperature>400 DEG C (preferably greater than or equal to 440 DEG C), impact is strong
Degree>20KJ/m2, can be applied to Aero-Space main force support structure/time load-carrying construction.
4) the invention also discloses the high-ductility bimaleimide resin and its preparation method of solidified resin, two kinds of trees
The preparation method of fat is safe and simple, efficient.
5) the composite CAI values that the present invention uses bismaleimide resin to be prepared for matrix are more than 230MPa, even up to
240MPa, can meet aerospace structure part use requirement.
Embodiment
General formula compound of the present invention and its preparation method and application is done further below in conjunction with specific embodiment
Detailed description.The following example is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as to present invention protection
The limitation of scope.In the range of all technologies realized based on the above of the present invention are encompassed by it is contemplated that protecting.
Unless otherwise indicated, the raw material and reagent used in following examples is commercial goods, or can be by
It is prepared by perception method.
Embodiment 1
Equipped with agitator, 40g diallyl bisphenols are added in the three-necked flask of thermometer and reflux condensing tube, slowly
110 DEG C are warming up to, 20g 2- methyl isophthalic acids, 5- dimaleoyl iminos benzene and 20g N, N ' -4,4 ' hexichol are added after temperature stabilization
Methane BMI, 110 DEG C of isothermal reactions are cooled to 80 DEG C to resin system transparent and homogeneous, add 3g TDE-85,2g
PEG (molecular weight 10000) and 0.2g TEMPO, the low softening of high tenacity is obtained after being stirring evenly and then adding into 20g PI, stirring 30min
The bimaleimide resin of point, resin is that khaki is semi-solid.
Glued membrane is made in the bimaleimide resin prepared using adhesive film machine, then compounds and makes with T300 carbon fibers
Standby prepreg, composite is prepared using mould pressing process.
Embodiment 2
Equipped with agitator, 30g diallyl bisphenols are added in the three-necked flask of thermometer and reflux condensing tube, slowly
110 DEG C are warming up to, 25g 2- methyl isophthalic acids, 5- dimaleoyl iminos benzene and 30g N, N ' -4,4 ' hexichol are added after temperature stabilization
Methane BMI, 110 DEG C of isothermal reactions are cooled to 80 DEG C to resin system transparent and homogeneous, add 5g AG80,2g
KH550 and 0.2g BHT, are stirring evenly and then adding into the span that high tenacity low softening point is obtained after 15g PEK-C, stirring 30min
Imide resin, resin is that khaki is semi-solid.
Embodiment 3
Equipped with agitator, 50g diallyl bisphenols are added in the three-necked flask of thermometer and reflux condensing tube, slowly
110 DEG C are warming up to, 15g 2,2 '-bis- [4- (4- maleimide phenoxyls) phenyl] propane and 25g are added after temperature stabilization
N, N ' -4,4 ' diphenyl methane dimaleimides, 110 DEG C of isothermal reactions are cooled to 80 DEG C, addition to resin system transparent and homogeneous
3g TDE-85,4g PEG (molecular weight 20000) and 0.3g 1,1- diphenylethlene, are stirring evenly and then adding into 10g PI, stirring
The bimaleimide resin of high tenacity low softening point is obtained after 30min, resin is that khaki is semi-solid.
Embodiment 4
Equipped with agitator, 40g diallyl bisphenols are added in the three-necked flask of thermometer and reflux condensing tube, slowly
110 DEG C are warming up to, 10g 2- methyl isophthalic acids, 5- dimaleoyl iminos benzene and 34g N, N ' -4,4 ' hexichol are added after temperature stabilization
Methane BMI, 110 DEG C of isothermal reactions are cooled to 80 DEG C to resin system transparent and homogeneous, add 6g AG80,2g
KH550 and 0.2g TEMPO, are stirring evenly and then adding into the span that high tenacity low softening point is obtained after 12g PEK-C, stirring 30min
Bismaleimide resin, resin is that khaki is semi-solid.
Glued membrane is made in obtained bimaleimide resin produced above using adhesive film machine, it is then multiple with T300 carbon fibers
With prepreg is prepared, composite is prepared using mould pressing process.
Embodiment 5
Equipped with agitator, 35g diallyl bisphenols are added in the three-necked flask of thermometer and reflux condensing tube, slowly
110 DEG C are warming up to, 10g 2,2 '-bis- [4- (4- maleimide phenoxyls) phenyl] propane, 10g are added after temperature stabilization
3- allyloxy list maleimides and 30g N, N ' -4,4 ' diphenyl methane dimaleimides, 110 DEG C of isothermal reactions to resin
System transparent and homogeneous, are cooled to 80 DEG C, add 5g TDE-85 and 3g P200, are stirring evenly and then adding into 15g PES, stir
The bimaleimide resin of high tenacity low softening point is obtained after 30min, resin is that khaki is semi-solid.
Embodiment 6
The embodiment 1-5 high tenacity bimaleimide resins prepared are poured into the steel mould of customization, at 140 DEG C
It is placed in vacuum drying chamber and takes out 10-40 minutes.Until system bubble-free.
Embodiment 7
In the steel mould that the resin prepared in embodiment 6 is poured into customization, it is subsequently placed in Constant Temp. Oven and divides
Section solidification.Solidifying temperature-rise period is：140 DEG C/2h, 180 DEG C/2h, 210 DEG C/6h.Obtain high tenacity BMI solidification tree
Fat, its softening point is 52 DEG C, and glass transition temperature is 250-260 DEG C, heat decomposition temperature>400 DEG C, impact strength>20KJ/m2, it is curved
Qu Qiangdu is 130MPa,
Embodiment 8
The carbon fibre composite that will be prepared in embodiment 1 and 4, through 140 DEG C/2h in press, 180 DEG C/2h, 210 DEG C/
The high-ductility span based composites of fibre reinforced are obtained after 6h solidifications.Composite CAI is up to 240MPa.
The specific test data of embodiment 7 and embodiment 8 is listed in Table 1 below.
Table 1
From the result of such as upper table 1, the bismaleimide resin of preparation is a kind of collection heat resistance, mechanical property and processing characteristics
In the high performance resin of one, its heat decomposition temperature is all higher than 440 DEG C, while the impact strength of pour mass (i.e. solidified resin) is equal
More than 20KJ/m2, wherein maximum 30KJ/m2, it is on close level with epoxy resin.Use that bismaleimide resin prepared for matrix is compound
Material C AI values are more than 230MPa, or even up to 240MPa, meet aerospace structure part use requirement.
More than, embodiments of the present invention are illustrated.But, the present invention is not limited to above-mentioned embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution and improvements done etc., should be included in the guarantor of the present invention
Within the scope of shield.
Claims (10)
1. a kind of bismaleimide amine composition for preparing bimaleimide resin, it is characterised in that the composition includes
The component of following parts by weight：
Wherein, the bismaleimide monomer, allyl compound, the parts by weight sum of thermoplasticity macromolecular are 100 parts；It is many
The parts by weight of functional epoxy resins are relative to the weight of bismaleimide monomer, allyl compound and thermoplasticity macromolecular
For part sum.
2. bismaleimide amine composition according to claim 1, it is characterised in that the composition also includes 0.1-10
The surface modifier of part, the parts by weight of surface modifier are relative to bismaleimide monomer, allyl compound and thermoplastic
For the parts by weight sum of property macromolecular.
Preferably, the composition still further comprises 0.1-2 parts of free radical scavenger, and the parts by weight of free radical scavenger are
For the parts by weight sum of bismaleimide monomer, allyl compound and thermoplasticity macromolecular.
3. bismaleimide amine composition as claimed in claim 1 or 2, it is characterised in that the bismaleimide monomer
Selected from N, N ' -4,4 ' diphenyl methane dimaleimides, 2- methyl isophthalic acids, 5- dimaleoyl iminos benzene, 2,2 '-bis- [4- (4- horses
Carry out imide phenoxy group) phenyl] one or more in propane or 3- allyloxy list maleimides.
Preferably, the bismaleimide monomer is the combination of two groups of monomers, and first group of monomer is selected from N, N ' -4,4 ' hexichol first
Alkane BMI, second group of monomer is selected from 2- methyl isophthalic acids, 5- dimaleoyl iminos benzene, 2,2 '-bis- [4- (4- Malaysias acyls
Imines phenoxyl) phenyl] propane or one kind in 3- allyloxy list maleimides, two or three.
It is further preferred that the bismaleimide monomer is selected from N, N ' -4,4 ' diphenyl methane dimaleimides and 2- first
The mixture or N, N ' -4,4 ' diphenyl methane dimaleimide and 3- allyloxys of base -1,5- dimaleoyl imino benzene
The mixture or N, N ' -4,4 ' diphenyl methane dimaleimide of single maleimide, 2,2 '-bis- [4- (4- maleimides
Phenoxyl) phenyl] propane and 3- allyloxy list maleimides mixture.
Preferably, the parts by weight of the bismaleimide monomer are 40-60 parts.
It is further preferred that when the bismaleimide monomer is the combination of two groups of monomers, with bismaleimide monomer
Gross weight meter, the percentage by weight of first group of monomer is 20-90wt%, and the percentage by weight of second group of monomer is 10-
80wt%.It is further preferred that the percentage by weight of first group of monomer is 50-80wt%, the percentage by weight of second group of monomer is 20-
50wt%.
Preferably, the allyl compound is selected from diallyl bisphenol, diallyl bisphenol ether, hexafluoro diallyl bis-phenol
One or more in A, diallyl bisphenol S or chavicol.
Preferably, the parts by weight of the allyl compound are 20-50 parts.
Preferably, the thermoplasticity macromolecular is selected from PEI (PEI), polyether sulfone (PES), polyphenylene oxide (PPO), polyamides Asia
Amine (PI), polyether-ether-ketone (PEEK), one kind in PAEK (PEK-C) or its a variety of combination.Preferably, the thermoplasticity
The parts by weight of macromolecular are 5-20 parts.
Preferably, the polyfunctional epoxy resin be selected from 4,5- oxepanes -1,2- dicarboxylic acid diglycidyl ester (TDE-85),
4,4 '-MDA epoxy resin (AG80), one kind in ammonia phenolic group trifunctional epoxy resin (AFG90) or its is a variety of
Combination.
Preferably, the parts by weight of the polyfunctional epoxy resin are 3-8 parts.
Preferably, the surface modifier is selected from aminopropyl triethoxysilane (KH550), γ-(2,3- the third oxygen of epoxy) propyl group
Trimethoxy silane (KH560), vinyltrimethoxy silane (A171), polyethylene glycol (PEG, molecular weight 10000 or
20000) one kind, in ethylene oxide polymer (molecular weight 10000 or 20000 is respectively designated as P100, P200) or its is a variety of
Combination.Preferably, the parts by weight of the surface modifier are 1-5 parts.
Preferably, the free radical scavenger be selected from 2,2,6,6- tetramethyl piperidine oxides (TEMPO), 2,6- di-t-butyls-
One or more in 4- methylphenols (BHT), 1,1- diphenylethlenes and 1,4- cyclohexadiene.
Preferably, the parts by weight of the free radical scavenger are 0.1-1 parts.
4. a kind of bimaleimide resin, it is characterised in that the resin by the span described in claim any one of 1-3 Lai
Acid imide composition is obtained by blending reaction.
Preferably, the softening point of the bimaleimide resin is 40-60 DEG C, and viscosity is 3-6Pas at 130 DEG C.
Preferably, the pour mass of the bimaleimide resin is the impact strength of solidified resin>20J/m2, the resin-made
Standby composite CAI values are more than 230MPa.
5. the preparation method of bimaleimide resin as claimed in claim 4, it is characterised in that methods described includes following step
Suddenly：By the bismaleimide monomer in the bismaleimide amine composition, allyl compound heating stirring to transparent, drop
Polyfunctional epoxy resin and optional ground surfactant and/or free radical scavenger are added after temperature, stirring is eventually adding thermoplasticity
Macromolecular, stirs and obtains the bimaleimide resin.
6. the preparation method of bimaleimide resin as claimed in claim 5, it is characterised in that the temperature of the heating stirring
Between 110~150 DEG C, such as 110 DEG C.
Preferably, the cooling is that the temperature of reaction system is down between 80-100 DEG C, for example, be cooled to 80 DEG C.
Preferably, stirring after polyfunctional epoxy resin and optional ground surfactant and/or free radical scavenger is added extremely to dissolve.
Preferably, it is 10-30min to add mixing time after thermoplasticity macromolecular.
7. a kind of BMI solidified resin, it is characterised in that it is by solidifying BMI described in claim 4
Resin and obtain.
Preferably, the temperature-rise period that uses of solidifying can be for：140 DEG C/2h, 180 DEG C/2h, 210 DEG C/6h.
Preferably, the glass transition temperature of the solidified resin is more than 250 DEG C, heat decomposition temperature>400 DEG C (preferably greater than or equal to
440 DEG C), impact strength>20KJ/m2。
8. the preparation method of BMI solidified resin as claimed in claim 7, it is characterised in that comprise the following steps：
1) bimaleimide resin as described above is prepared；
2) by step 1) obtained bimaleimide resin solidified.
Preferably, step 1) in, preparing the method for bimaleimide resin as described above has as in claim 5 or 6
Defined operating procedure.
Preferably, step 2) in, the temperature-rise period that the solidification is used has the definition described in claim 7.
9. a kind of prepreg, it is characterised in that it includes the bimaleimide resin described in claim 4.
Preferably, reinforcing fiber is also included in the prepreg.
Preferably, the reinforcing fiber can be carbon fiber, such as T300 carbon fibers.
Preferably, in the prepreg, the parts by weight of bimaleimide resin are 35-40 parts；The parts by weight of the carbon fiber
For 60-65 parts.
10. a kind of composite, it is prepared as the prepreg described in claim 9.
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