CN107163575A - A kind of bismaleimide resin LCM composite material preformed body setting agents and preparation method thereof - Google Patents
A kind of bismaleimide resin LCM composite material preformed body setting agents and preparation method thereof Download PDFInfo
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- CN107163575A CN107163575A CN201710359502.7A CN201710359502A CN107163575A CN 107163575 A CN107163575 A CN 107163575A CN 201710359502 A CN201710359502 A CN 201710359502A CN 107163575 A CN107163575 A CN 107163575A
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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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 present invention relates to a kind of bismaleimide resin LCM composite material preformed body setting agents and preparation method thereof.The setting agent is made up of bimaleimide resin, epoxy resin, the agent of allylic process modification, thickener and plasticized modifier.The setting agent preparation technology of the present invention is simple, and reaction condition is more gentle controllable, reduces the production cost of setting agent powder；The setting agent setting temperature low time is short, reduces equipment energy consumption and shortens the preform process-cycle, effectively the manufacturing cost of reduction labyrinth large-scale product precast body；While resistant, toughened dose that its system contains, inorganic particulate thickener can improve Tg, prevent that powder is hardened in setting agent storage process, and improve setting agent scour resistance, while fixed effect is ensured, effective dose is reduced to the 3%~5% of fabric surface density, the permeability of precast body is improved, flow resistance when reducing resin infiltration, and prevent excessive setting agent to cause the problem of system glass transition temperature is reduced.
Description
Technical field
The invention belongs to LCM manufacture technology of composite material field, it is related to a kind of bismaleimide resin LCM composite material preformed bodies
Setting agent and preparation method thereof.
Background technology
Liquid composite molding technology (LCM) technology is the class developed rapidly after 1980s
High-performance and low-cost manufacturing technology, has been increasingly becoming the main flow of Modern Composite Materials scientific and engineering development, and forms
With a series of high-performance and low-cost advanced composite material manufacturing technologies including the techniques such as RTM, VARI and RFI.
Bismaleimide resin (BMI) is as a class advanced composite material matrix, by high temperature resistant, radioresistance, wet-heat resisting and low suction
The advantages of wet rate, show one's talent in the competition with similar resin, be widely used in the high-tech areas such as Aeronautics and Astronautics.Especially
It is the combination of Liquid molding techniques and composite labyrinth integral fabrication technique, makes bismaleimide resin in labyrinth product
Application aspect is further expanded, when preparing composite material component for F-22 bird of prey fighter planes, because Qing Te companies are big using RTM
Mass production processes, thus can disposably prepare up to 400 high intensity, the CYCOM 5250-4 spans of low tolerance carry out acyl
Imide resin based composites part, substantially increases structural intergrity and military service performance.
The country is in the late 1980s in order to adapt to the need for new fighter plane develops, start compound to advanced BMI
Material resin matrix is studied, and obtains a series of important scientific achievements.The BMI resins of current commercialization mainly have
QY8911, QY9611,5405,5428,5429 and 6421 etc..The Hes of QY8911- IV researched and developed by Beijing Research Inst. of Aeronautic Material
6421 be RTM moulding process resins, wherein 6421 applications are wider, with preferable toughness, comprehensive mechanical property is excellent, can be used for
Aircraft main force support structure, engine component and missile airframe etc..
For liquid molding composite labyrinth integral fabrication technique, composite element form accuracy and size essence
The near net type of degree is the important symbol of Modern Manufacturing Technology level.Because fabric and its precast body are generally in laid course
Existing soft fluffy state, the ability with Nonlinear Large Deformation under pressure, and there is the limit of deformation, so this deformation must be studied
The relation of ability and near net type, and by special shaping material, certain prefabrication state is fixed, therefore this technology and quilt
Referred to as pre-setting technology, and the auxiliary material for being used for pre-setting is referred to as setting agent.
Preform technique is usually thin layer individual layer part to be made in advance, then lay design in a mold with this individual layer part
Simultaneously overall structure fiber preform body is made in the number of plies.The key of this technology be select not only there is enough adhesion but also with resin phase
The setting agent of appearance.It is to sizing, infiltration, infiltration and compatible etc. plays conclusive effect.Its main function is to bond fiber
Together, keep preform shape, prevent fiber from washing away deformation in injecting resin.Only using suitable setting agent to knitting
Thing and its structure progress are prefabricated, can just obtain near net-shaped preform.
Setting agent is preformed in be overcome the shortcomings of or compensate for weave preform technique to a certain extent, to quality requirement
Height, performance is stable, and baroque product is particularly important, the complex-shaped massive article of the preparation structure that is particularly suitable for use in, and is protecting
Demonstrate,prove product quality, shortening production cycle and automation aspect significant, be the effective way of cost degradation.
But the styling aid products suitable for bismaleimide resin of commercialization both at home and abroad are less at present.Foreign countries' report is more
The preform setting agent CYCOM 782RTM that bismaleimide resin is developed are directed to for Cytec companies, can be with 5250-4RTM, 5280-
The bismaleimide resin matrix such as 1RTM and 824RTM is used in combination.The country only has Beijing Research Inst. of Aeronautic Material to coordinate 6421 resins to develop
Setting agent ES-T541, be solid-state under the setting agent normal temperature, acetone solvent can be dissolved in and be prepared into solution shape setting agent, and
Powdered setting agent can be prepared into.But existing span setting agent setting temperature is higher, typically 100~120 DEG C/15~
It is preforming under 30min, if setting agent setting temperature can be reduced and shorten shaping time, it will further decrease equipment energy consumption simultaneously
Shorten the preform process-cycle, be more beneficial to reduce the manufacturing cost of labyrinth large-scale product precast body.Also, tradition
Span setting agent preparation method to select a kind of epoxy resin elder generation and diallyl under 180 DEG C~200 DEG C of hot conditions
Bisphenol-a reaction improves molecular weight, then cools to 150 DEG C, adds BDM type span monomer reactions, obtains the pre-polymerization of certain molecular weight
Thing as setting agent, due to will prepolymerization twice at high temperature, its preparation technology is complicated and temperature is higher, and generally multigroup
Point, powdered finished product need to be remixed into after pulverizer is crushed respectively, be unfavorable for the control of technical process and cost is high.Separately
Outside, in order to reach good fixed effect, the consumption of existing composite enhancing fabric setting agent accounts for matrix resin consumption
8%-15%, because setting agent occupies the hole inside fiber preform, reduces the permeability of precast body, adds resin leaching
Flow resistance during profit, and excessive setting agent often leads to the reduction of system glass transition temperature.
The content of the invention
The purpose of the present invention is：A kind of bismaleimide resin LCM composite material preformed body setting agents and preparation method thereof are proposed,
To improve sizing agent producing process, production cost is reduced；Reduce setting agent setting temperature and shorten shaping time, reduce equipment energy
Consume and shorten the preform process-cycle, reduce the manufacturing cost of labyrinth large-scale product precast body；And solve existing sizing
The consumption that agent is present is big, and setting agent occupies the hole inside fiber preform, reduces the permeability of precast body, adds resin
Flow resistance during infiltration, and excessive setting agent is the problems such as cause the reduction of system glass transition temperature.
Specifically, the technical solution adopted by the present invention is as follows：
A kind of bismaleimide resin LCM composite material preformed body setting agents, it is by the span that mass fraction is 20-40 parts is come acyl
Imide resin, 20-30 parts of epoxy resin, 20-40 parts of allylic process modification agent, 0-5 parts of thickener, 5-15 parts
Plasticized modifier is constituted.
Described bimaleimide resin is by N, N '-(4,4 '-methylenediphenyl) BMI (MDA-
BMI), N, N '-(4- methyl isophthalic acids, 3- phenylenes)-BMI (TDA-BMI), 2,2,4- trimethyl -1,6- hexamethylene diamines
Aliphatic BMI (TMH-BMI), 2,2- bis- [4- (4- maleimides phenoxy group) phenyl] propane (BMP-BMI)
In it is one or more more than composition according to proper proportion combination.
Bisphenol type epoxy tree of the epoxy resin for combination softening point between 50 DEG C -100 DEG C selected by above-mentioned setting agent
Fat, bisphenol f type epoxy resin, bisphenol-s epoxy resin, many phenolic tetraglycidel ether epoxy resins, aliphatic glycidyl ether
Type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, cycloaliphatic epoxy resin, heterocyclic type ring
Oxygen tree fat, cresol-novolak type epoxy resin, phenol novolac type epoxy resin, they containing halogen, nitrogenous, phosphorous, siliceous flame-retardant modified
More than one or more in compound, and their nuclear hydrogenation compound composition according to proper proportion combination.Preferably
Be conducive to improving the epoxy resin of setting agent adhesiveness and the group of the higher phenol aldehyde type epoxy resin of heat resistance containing structures such as-OH
Compound.
Allylic process modification agent selected by above-mentioned setting agent is diallyl bisphenol, diallyl bisphenol S, neighbour,
It is adjacent '-diisopropenyl bisphenol-A, tetrabutyl ammonium bromide, pi-allyl eugenol, chavicol, allyl benzene cresols, allyl
More than one or more in base ether phenolic resin etc. composition according to proper proportion combination.
Thickener selected by above-mentioned setting agent is aerosil, precipitated silica, organobentonite, kaolinite
One or more of combinations according to proper proportion in soil, attapulgite etc..Preferably nano fumed silica, it is in sizing
In agent system it is dispersed after, a silica aggregate network, the silanol base (Si- that aggregation passes through surface can be formed
OH) with polymer molecule formation hydrogen bond, it is restricted the mobility of system, the viscosity increase of system, so as to play thickening
Effect, so as to effectively prevent from declining its fixed effect caused that washes away in liquid resin processes after product approval.While gas
The particle diameter of aerosil is small, surface area is big, surface silanol groups (Si-OH) more and its aggregation three-dimensional branched structure, pass through
Hydrogen bond or Van der Waals force cause between silica and polymer molecule, produce forceful action between silicon dioxide molecules, are carrying
Activeness and quietness can be reached while for thickening property, and improves Tg effect.
Plasticized modifier selected by above-mentioned setting agent is polyether sulfone (PES), PAEK (PEK-C), polyether-ether-ketone
(PEEK), one or more above thermoplastic resins in PEI (PEI), TPI (TPI) are by certain
The combination of ratio.The preferably higher TPI of heat resistance (TPI).
The preparation method of setting agent as described above, specific preparation process is as follows：
(1) 20-40 parts of bimaleimide resin, 20-30 parts of epoxy resin, 20-40 is weighed according to mass fraction
The allylic process modification agent of part, 0-5 parts of thickener, 5-15 parts of plasticized modifier；
(2) epoxy resin weighed in step one, the agent of allylic process modification and plasticized modifier are added to mixing
100-130 DEG C, insulated and stirred are heated in device or reactor under stirring until resin is completely dissolved to form transparent
Solution；
(3) bimaleimide resin and thickener are added in the solution of above-mentioned steps two, added under stirring
Heat is warming up to 130-140 DEG C, and insulated and stirred dissolves bimaleimide resin, continues insulated and stirred and is supervised by instrument and equipment
Survey melt viscosity to control the prepolymerization reaction degree of allyl compound and span monomer, discharged after proper viscosity is reached, i.e.,
Obtain the setting agent resin for solid-state under normal temperature；
(4) gained setting agent resin in step 3 is added in mechanical crusher, freezing crusher or airslide disintegrating mill
The granularity of 60-100 mesh is crushed to, that is, obtains the setting agent powder-product for solid-state under normal temperature.
The invention has the advantages that：Setting agent preparation technology is simple, only in the pre-polymerization of 130-140 DEG C of process
Close, reaction condition is more gentle controllable, and setting agent only by a pulverizing processing, simplifies setting agent process, reduced
The production cost of setting agent powder；Setting agent is preforming under 70~90 DEG C/15~25min, reduces setting agent setting temperature,
And shorten shaping time, reduce equipment energy consumption and shorten the preform process-cycle, be more beneficial to reduction labyrinth big
The manufacturing cost of type product precast body；Contain resistant, toughened dose of its system simultaneously, inorganic particulate thickener can improve Tg,
Prevent that powder is hardened in setting agent storage process, and improve setting agent scour resistance, will be effective while fixed effect is ensured
Consumption reduces the 3%~5% of fabric surface density, improves the permeability of precast body, flow resistance when reducing resin infiltration, and
And prevent excessive setting agent to cause the reduction problem of system glass transition temperature.
The present invention setting agent matrix material therefor for liquid molding bismaleimide resin often use raw material, it is ensured that setting agent and
The compatibility of bismaleimide resin, meets type approval requirements of the bismaleimide resin LCM composites to preform, is expected in aviation, boat
The field such as it bismaleimide resin LCM composite material structural member precast bodies manufacture view obtains extensive use.
Embodiment
The present invention is described in further details below.A kind of bismaleimide resin LCM composite material preformed body setting agents, its
Be characterised by, its by mass fraction be 20-40 parts of bimaleimide resin, 20-30 parts of epoxy resin, 20-40 parts
The agent of allylic process modification, 0-5 parts of thickener, 5-15 parts of plasticized modifier composition.
Bimaleimide resin be by N, N '-(4,4 '-methylenediphenyl) BMI (MDA-BMI), N,
N '-(4- methyl isophthalic acids, 3- phenylenes)-BMI (TDA-BMI), the aliphatic series of 2,2,4- trimethyl -1,6- hexamethylene diamines is double
In maleimide (TMH-BMI), 2,2- bis- [4- (4- maleimides phenoxy group) phenyl] propane (being designated as BMP-BMI)
It is one or more more than composition according to proper proportion combination.
Bisphenol type epoxy tree of the epoxy resin for combination softening point between 50 DEG C -100 DEG C selected by above-mentioned setting agent
Fat, bisphenol f type epoxy resin, bisphenol-s epoxy resin, many phenolic tetraglycidel ether epoxy resins, aliphatic glycidyl ether
Type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, cycloaliphatic epoxy resin, heterocyclic type ring
Oxygen tree fat, cresol-novolak type epoxy resin, phenol novolac type epoxy resin, they containing halogen, nitrogenous, phosphorous, siliceous flame-retardant modified
More than one or more in compound, and their nuclear hydrogenation compound composition according to proper proportion combination.Preferably
Be conducive to improving the epoxy resin of setting agent adhesiveness and the group of the higher phenol aldehyde type epoxy resin of heat resistance containing structures such as-OH
Compound.
Allylic process modification agent selected by above-mentioned setting agent is diallyl bisphenol, diallyl bisphenol S, neighbour,
It is adjacent '-diisopropenyl bisphenol-A, tetrabutyl ammonium bromide, pi-allyl eugenol, chavicol, allyl benzene cresols, allyl
More than one or more in base ether phenolic resin etc. composition according to proper proportion combination.
Thickener selected by above-mentioned setting agent is aerosil, precipitated silica, organobentonite, kaolinite
One or more of combinations according to proper proportion in soil, attapulgite etc..Preferably nano fumed silica, it is in sizing
In agent system it is dispersed after, a silica aggregate network, the silanol base (Si- that aggregation passes through surface can be formed
OH) with polymer molecule formation hydrogen bond, it is restricted the mobility of system, the viscosity increase of system, so as to play thickening
Effect, so as to effectively prevent from declining its fixed effect caused that washes away in liquid resin processes after product approval.While gas
The particle diameter of aerosil is small, surface area is big, surface silanol groups (Si-OH) more and its aggregation three-dimensional branched structure, pass through
Hydrogen bond or Van der Waals force cause between silica and polymer molecule, produce forceful action between silicon dioxide molecules, are carrying
Activeness and quietness can be reached while for thickening property, and improves Tg effect.
Plasticized modifier selected by above-mentioned setting agent is polyether sulfone (PES), PAEK (PEK-C), polyether-ether-ketone
(PEEK), one or more above thermoplastic resins in PEI (PEI), TPI (TPI) are by certain
The combination of ratio.The preferably higher TPI of heat resistance (TPI).
The preparation method of setting agent as described above, it is characterised in that specific preparation process is as follows：
(1) 20-40 parts of bimaleimide resin, 20-30 parts of epoxy resin, 20-40 is weighed according to mass fraction
The allylic process modification agent of part, 0-5 parts of thickener, 5-15 parts of plasticized modifier；
(2) epoxy resin weighed in step one, the agent of allylic process modification and plasticized modifier are added to mixing
100-130 DEG C, insulated and stirred are heated in device or reactor under stirring until resin is completely dissolved to form transparent
Solution；
(3) bimaleimide resin and thickener are added in the solution of above-mentioned steps two, added under stirring
Heat is warming up to 140 DEG C, and insulated and stirred dissolves bimaleimide resin, continues insulated and stirred and is monitored by instrument and equipment molten
Body viscosity controls the prepolymerization reaction degree of allyl compound and span monomer, discharges, that is, obtains after proper viscosity is reached
It is the setting agent resin of solid-state under normal temperature；
(4) gained setting agent resin in step 3 is added in mechanical crusher, freezing crusher or airslide disintegrating mill
The granularity of 80 mesh is crushed to, that is, obtains the setting agent powder-product for solid-state under normal temperature.
The present invention basic functional principle be：Choose bimaleimide resin and allyl compound be as main body into
Point, the Miscibility of increase setting agent and span liquid resin, improving setting agent adhesiveness using epoxy resin improves sizing
Allyl compound, epoxy resin and toughener, are partly dissolved, then bimaleimide resin is added thereto by effect first
Prepolymerization is carried out with allyl compound, improves molecular weight to ensure that final product has suitable softening point, is easy to processing
Crush.Due to system epoxy resin be individualism not with allyl compound high temperature pre-polymerization so that setting agent prepare temperature
Degree reduction, and the addition of thickener and toughener component adds system viscosity, improves system softening point, it is to avoid powder at room temperature
Broken rear setting agent is hardened, and improves the scour resistance of setting agent at a temperature of LCM technique injecting glues；In addition, epoxy resin, toughener and
While the addition of thickener ingredients make it that setting temperature is reduced, the setting agent usage amount reduction of identical fixed effect is obtained, together
When the toughener chosen and thickener there is higher temperature tolerance, it is ensured that the Tg of bismaleimide resin system.
Below will be by specific embodiment come the present invention is described in detail, but the present invention is not limited to following implementations
Example, in addition to it is any appropriately combined between embodiment.
[embodiment 1]
A kind of bismaleimide resin LCM composite material preformed body setting agents, it is 35 parts of bismaleimide by mass fraction
Polyimide resin, 27 parts of epoxy resin, 30 parts of allylic process modification agent, 2 parts of thickener, 10 parts of plasticized modifier group
Into.
Bimaleimide resin selected by above-mentioned setting agent is N, and N '-(4,4 '-methylenediphenyl) span carrys out acyl
Imines (MDA-BMI).Selected epoxy resin for bisphenol A type epoxy resin of the combination softening point between 50 DEG C -100 DEG C and
Phenol novolac type epoxy resin according to proper proportion combination.Selected allylic process modification agent is diallyl bisphenol.
Selected thickener is aerosil.Selected plasticized modifier is the higher TPI of heat resistance
(TPI)。
The preparation method of setting agent as described above, specific preparation process is as follows：
(1) 35 parts of bimaleimide resin, 27 parts of epoxy resin, 30 parts of pi-allyl is weighed according to mass fraction
The agent of class process modification, 2 parts of thickener, 10 parts of plasticized modifier；
(2) epoxy resin weighed in step one, the agent of allylic process modification and plasticized modifier are added to mixing
100-130 DEG C, insulated and stirred are heated in device or reactor under stirring until resin is completely dissolved to form transparent
Solution；
(3) bimaleimide resin and thickener are added in the solution of above-mentioned steps two, added under stirring
Heat is warming up to 130-140 DEG C, and insulated and stirred dissolves bimaleimide resin, continues insulated and stirred and is supervised by instrument and equipment
Survey melt viscosity to control the prepolymerization reaction degree of allyl compound and span monomer, discharged after proper viscosity is reached, i.e.,
Obtain the setting agent resin for solid-state under normal temperature；
(4) gained setting agent resin in step 3 is added in mechanical crusher, freezing crusher or airslide disintegrating mill
The granularity of 60-100 mesh is crushed to, that is, obtains the setting agent powder-product for solid-state under normal temperature.
[embodiment 2]
The present embodiment is different from the part of embodiment 1：Selected bimaleimide resin is N, N '-(4- methyl isophthalic acids,
3- phenylenes)-BMI (TDA-BMI).Other are same as Example 1.
[embodiment 3]
The present embodiment is different from place of embodiment 1-2：Selected epoxy resin be softening point 50 DEG C -100 DEG C it
Between bisphenol A type epoxy resin.Other are identical with embodiment 1-2.
[embodiment 4]
The present embodiment is different from place of embodiment 1-3：Selected allylic process modification agent is that diallyl is double
Phenol A and diallyl bisphenol S and chavicol according to proper proportion combination.Other are identical with embodiment 1-3.
[embodiment 5]
The present embodiment is different from place of embodiment 1-4：Selected thickener is precipitated silica, organobentonite
Proper proportion combination.Other are identical with embodiment 1-4.
[embodiment 6]
The present embodiment is different from place of embodiment 1-5：Selected plasticized modifier is PAEK (PEK-C) and poly-
The combination of the proper proportion of etherimide (PEI).Other are identical with embodiment 1-5.
[embodiment 7]
The present embodiment is different from place of embodiment 1-6：By in preparation process three, it is heated under stirring
140 DEG C, it is adjusted to 130 DEG C.Other are identical with embodiment 1-6.
[embodiment 8]
The present embodiment is different from place of embodiment 1-7：Setting agent resin in preparation process four is added to mechanical crushing
The granularity of 80 mesh is crushed in machine, freezing crusher or airslide disintegrating mill, 100 mesh are adjusted to.Other are identical with embodiment 1-7.
[embodiment 9]
The present embodiment is different from place of embodiment 1-7：A kind of bismaleimide resin LCM composite material preformed body setting agents,
Its by mass fraction for 30 parts bimaleimide resin, 28 parts of epoxy resin, 30 parts of allylic process modification agent,
4 parts of thickener, 8 parts of plasticized modifier composition.Other are identical with embodiment 1-8.
Claims (7)
1. a kind of bismaleimide resin LCM composite material preformed body setting agents, it is characterised in that it is 20-40 parts by mass fraction
Bimaleimide resin, 20-30 parts of epoxy resin, 20-40 parts of allylic process modification agent, 0-5 parts of thickening
Agent, 5-15 parts of plasticized modifier composition.
2. bismaleimide resin LCM composite material preformed body setting agents as claimed in claim 1, it is characterised in that the span
Bismaleimide resin is by N, N '-(4,4 '-methylenediphenyl) BMI (MDA-BMI), N, N '-(4- methyl isophthalic acids,
3- phenylenes)-BMI (TDA-BMI), the aliphatic BMI of 2,2,4- trimethyl -1,6- hexamethylene diamines
(TMH-BMI), in 2,2- bis- [4- (4- maleimides phenoxy group) phenyl] propane (BMP-BMI) it is one or more into
The combination divided.
3. bismaleimide resin LCM composite material preformed body setting agents as claimed in claim 1, it is characterised in that the epoxy
Bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type epoxy of the resin for combination softening point between 50 DEG C -100 DEG C
Resin, many phenolic tetraglycidel ether epoxy resins, aliphatic glycidyl ether type epoxy resin, glycidyl ester type epoxy tree
Fat, glycidyl amine type epoxy resin, cycloaliphatic epoxy resin, heterocyclic-type epoxy resin, cresol-novolak type epoxy resin, phenol aldehyde
Type epoxy resin, they contain halogen, nitrogenous, phosphorous, siliceous flame-retardant modified compound, and their nuclear hydrogenation compound in
The combination of one or more compositions.
4. bismaleimide resin LCM composite material preformed body setting agents as claimed in claim 1, it is characterised in that the allyl
The agent of base class process modification is diallyl bisphenol, diallyl bisphenol S, neighbour, adjacent '-diisopropenyl bisphenol-A, bisphenol-A diene
One or more in propyl ether, pi-allyl eugenol, chavicol, allyl benzene cresols, allyl ether phenolic resin etc.
The combination of composition.
5. bismaleimide resin LCM composite material preformed body setting agents as claimed in claim 1, it is characterised in that the thickening
Agent is one or more of groups in aerosil, precipitated silica, organobentonite, kaolin, attapulgite etc.
Close.
6. bismaleimide resin LCM composite material preformed body setting agents as claimed in claim 1, it is characterised in that the toughness reinforcing
Modifying agent is polyether sulfone (PES), PAEK (PEK-C), polyether-ether-ketone (PEEK), PEI (PEI), thermoplasticity polyamides
One or more combinations in imines (TPI).
7. a kind of preparation method of bismaleimide resin LCM composite material preformed body setting agents, it is characterised in that preparation process is such as
Under：(1) 20-40 parts of bimaleimide resin, 20-30 parts of epoxy resin, 20-40 parts of alkene is weighed according to mass fraction
The agent of propyl group class process modification, 0-5 parts of thickener, 5-15 parts of plasticized modifier；(2) by the asphalt mixtures modified by epoxy resin weighed in step one
Fat, the agent of allylic process modification and plasticized modifier are added in blender or reactor to be heated under stirring
100-130 DEG C, insulated and stirred are until resin is completely dissolved to form clear solution；(3) by bimaleimide resin and thickener
In the solution for being added to above-mentioned steps two, 130-140 DEG C is heated under stirring, insulated and stirred makes bismaleimide
Polyimide resin dissolves, and continues insulated and stirred and monitors melt viscosity to control allyl compound and span monomer by instrument and equipment
Prepolymerization reaction degree, after proper viscosity is reached discharge, that is, obtain under normal temperature be solid-state setting agent resin；(4) by step
Gained setting agent resin is added to the grain that 60-100 mesh is crushed in mechanical crusher, freezing crusher or airslide disintegrating mill in three
Degree, that is, obtain the setting agent powder-product for solid-state under normal temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710359502.7A CN107163575A (en) | 2017-05-19 | 2017-05-19 | A kind of bismaleimide resin LCM composite material preformed body setting agents and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710359502.7A CN107163575A (en) | 2017-05-19 | 2017-05-19 | A kind of bismaleimide resin LCM composite material preformed body setting agents and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110294931A (en) * | 2019-06-26 | 2019-10-01 | 航天材料及工艺研究所 | A kind of bimaleimide resin base body and the preparation method and application thereof |
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| CN102504482A (en) * | 2011-09-29 | 2012-06-20 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of rigid nanoparticle interlayer modified liquid-state molded composite material |
| CN103756314A (en) * | 2013-12-17 | 2014-04-30 | 中航复合材料有限责任公司 | Preparation method of bismaleimide resin used for composite material liquid molding |
| CN106280445A (en) * | 2016-08-11 | 2017-01-04 | 江苏恒神股份有限公司 | A kind of liquid molding high tenacity bismaleimide resin and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504482A (en) * | 2011-09-29 | 2012-06-20 | 中国航空工业集团公司北京航空材料研究院 | Preparation method of rigid nanoparticle interlayer modified liquid-state molded composite material |
| CN103756314A (en) * | 2013-12-17 | 2014-04-30 | 中航复合材料有限责任公司 | Preparation method of bismaleimide resin used for composite material liquid molding |
| CN106280445A (en) * | 2016-08-11 | 2017-01-04 | 江苏恒神股份有限公司 | A kind of liquid molding high tenacity bismaleimide resin and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110294931A (en) * | 2019-06-26 | 2019-10-01 | 航天材料及工艺研究所 | A kind of bimaleimide resin base body and the preparation method and application thereof |
| CN110294931B (en) * | 2019-06-26 | 2021-11-16 | 航天材料及工艺研究所 | Bismaleimide resin matrix and preparation method and application thereof |
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