CN108409966A - A kind of modified bismaleimide resin and preparation method thereof suitable for resin transfer molding - Google Patents
A kind of modified bismaleimide resin and preparation method thereof suitable for resin transfer molding Download PDFInfo
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Abstract
The present invention provides a kind of modified bismaleimide resin and preparation method thereof suitable for resin transfer molding, and the melting point resin is low, viscosity is low, solidification temperature is low, heat resistance is good, dielectric properties are good, and processing technology is excellent, is suitable for RTM techniques.The preparation method includes the following steps that 1 allyl, 2 cyanic acid ester group benzene is heated to 130 160 DEG C by step 1, and bismaleimide monomer is added, and heat preservation carries out polymerisation, obtains homogeneous performed polymer；3 amino benzocyclobutenes are added in the performed polymer obtained to step 1 for step 2, and it is 110~140 DEG C to adjust temperature, and bismaleimide monomer is added, and heat preservation carries out polymerisation, obtains the modified bismaleimide resin suitable for resin transfer molding.
Description
Technical field
The invention belongs to composite matrix resin field of material technology, it is related to a kind of suitable for resin transfer molding
Modified bismaleimide resin and preparation method thereof.
Background technology
Contain in bismaleimide molecular structure there are two maleimide ring, since this height unsaturated structure makes admittedly
It is big to change post-crosslinking density, heat resistance is much better than epoxy resin, and small etc. with wet-heat resisting, radiation hardness, modulus height, coefficient of thermal expansion
Good characteristic.But non-modified bismaleimide monomer crystallinity is high, and fusing point is high, and difficult, solidification is dissolved in Conventional solvents
Brittleness is big afterwards, loses use value substantially.Therefore, it is necessary to be modified to it, its crystallinity is destroyed, reduces fusing point, improves tree
Fat processing technology improves resin toughness and dielectric properties.
In terms of composite material preparation process, Resin transfer molding (RTM) forming technique be a kind of relatively advanced liquid at
Type method, it is considered to be solve one of the important technology of the high cost problem of advanced composite material.It is more multiple that RTM is suitable for molding structure
Miscellaneous product, it is high for the selection flexibility ratio of reinforcing material, the designability of composite material can be given full play to, closed moulding can subtract
Few resin harmful components are to human injury, and product surface is highly polished, fiber content is high, good combination property.But RTM moldings pair
The processing technology of resin is put forward higher requirements：Melting point resin is low, general to require to be less than 100 DEG C；Resin melting viscosity is low, and one
As be advisable with 200~500cP, working life generally require be more than 6h；Resin is good to fiber wetness；Volatile matter is small.
Western countries take the lead in carrying out the study on the modification to bimaleimide resin, and release tens of kinds of modified spans successively
Bismaleimide resin, and part has been commercialized, and it is widely used in aerospace field.Currently, with Qing Te companies of the U.S. and Hensel
The bimaleimide resin that the company of stepping is produced is affected.China is to bimaleimide resin in high-performance composite materials
The research of aspect starts from last century the eighties, and by continuous technological innovation, break-through skill barrier also achieves certain grind
Study carefully achievement, as 625 Zhao's canals of aviation are gloomy, beam state of University Of Suzhou positive (being Northwestern Polytechnical University originally), chemistry institute of Chinese Academy of Sciences Zhao Tong classes
Topic group successfully develops the modified bismaleimide resin kind of a collection of high comprehensive performance, and realizes the commodity of certain kinds
Change or half be commercialized, pushed modified bismaleimide resin in terms of high-performance composite materials deeper into application study and
Application practice.
It is directed to modified bismaleimide resin, the resin variety suitable for RTM moulding process mainly has both at home and abroad：The U.S.
The 5250-4RTM of cyanogen spy (former Narmco), 5292 (XU292 of former Ciba-Geigy companies) of Huntsman Corporation, China's aviation
625 QY8911-IV and Chinese Academy of Sciences's chemistry allyl phenolic aldehyde modified bismaleimide resin etc..
5250-4RTM includes diphenyl-methane type span monomer (BDM), diallyl bisphenol (DABPA) and BMI-1,3-
Tri- components of tolyl, minimum viscosity is higher than 1000cP at 100 DEG C, and initial viscosity is about 800cP at 120 DEG C, relative to RTM techniques
For it is still higher.Glass transition temperature is 271 DEG C after 227 DEG C of solidification 4h, and heat resistance is weakened.
5292 are modified the resin variety of BDM for DABPA, using most typical allyl compound modified bismaleimide
The method of resin.Viscosity is less than 1000cP, the modified bismaleimide tree that different DABPA/BDM ratios obtain at 100 DEG C
Glass transition temperature Tg is 218-234 DEG C after fat cures 10h at 200 DEG C.The DABPA/BDM of lower temperature pre-polymerization tends to have crystallization analysis
Go out, bin stability is bad.According to higher temperature pre-polymerization, then viscosity promotion can be caused possibly even to generate a small amount of gel.
QY8911-IV uses the compound modified span monomer of allyl phenols, and performed polymer molecular weight is relatively low, resin viscosity
Low, a DEG C viscosity is held at 500cP hereinafter, processing technology is good from 85 DEG C to 130.But due to resin system unsaturated group
Content is relatively low, and heat resistance is affected after solidification.
The Chinese Academy of Sciences chemistry institute the phenol aldehyde modified bimaleimide resin of allyl etherization be also relative maturity kind, this
Modified bismaleimide resin system has excellent building-up property, glass transition temperature Tg after solidification>350℃.But body
Solidification temperature is higher needed for system, reaches 250 DEG C, and unstability existing for allyl etherization phenolic aldehyde itself, the to a certain degree upper limit
Its application is made.
It can be seen that suitable for the commercialization modified bismaleimide resin kind of RTM, there are still each in performance at present
From the shortcomings that, it is difficult to take into account the holding of heat resistance and the improvement of processing technology, and be situated between to bimaleimide resin
Electrical property is pointedly promoted and to evaluate done research work less.Therefore, it is necessary to develop a kind of in guarantee curing system
While heat resistance and high-modulus, the features such as but also with low dielectric, low dielectric loss, low melting point, low melt viscosity, high curing reactivity
Modified bismaleimide resin especially suitable for RTM techniques.
Invention content
For problems of the prior art, the present invention provides a kind of modification span suitable for resin transfer molding
Bismaleimide resin and preparation method thereof, the melting point resin is low, viscosity is low, solidification temperature is low, heat resistance is good, dielectric properties
Good, processing technology is excellent, is suitable for RTM techniques.
The present invention is to be achieved through the following technical solutions：
A kind of preparation method of modified bismaleimide resin suitable for resin transfer molding, including walk as follows
Suddenly,
1- allyl -2- cyanic acid ester group benzene is heated to 130~160 DEG C, bismaleimide monomer is added by step 1,
Heat preservation is reacted, and homogeneous performed polymer is obtained；
3- amino benzocyclobutenes are added in the performed polymer obtained to step 1 for step 2, and it is 110~140 to adjust temperature
DEG C, bismaleimide monomer is added, heat preservation is reacted, and the modified bismaleimide suitable for resin transfer molding is obtained
Polyimide resin.
Preferably, in step 1,1- allyl -2- cyanic acid ester group benzene is heated to 130~160 DEG C, in 1 hour slowly
Bismaleimide monomer is added, insulation reaction 1-3 hours at this temperature, obtains homogeneous performed polymer.
Preferably, which is characterized in that in step 1,1- allyl -2- cyanic acid ester group benzene and bismaleimide monomer
Mass ratio is 1：(1.5~2.5).
Preferably, which is characterized in that in step 1, bismaleimide monomer has following structure,
Wherein, R is-CH2-、-O-、-SO2Or-O-Ph-C (CH3)2-Ph-O-。
Preferably, which is characterized in that in step 2, the performed polymer that step 1 is obtained cools down 20 DEG C or more, and 3- ammonia is added
Base benzocyclobutene, it is 110~140 DEG C to adjust temperature, bismaleimide monomer is slowly added in 1 hour, in this temperature
Lower insulation reaction 1~3 hour obtains the modified bismaleimide resin suitable for resin transfer molding.
Preferably, which is characterized in that in step 2, bismaleimide monomer has following structure,
Wherein, R is-CH2-、-O-、-SO2Or-O-Ph-C (CH3)2-Ph-O-。
Preferably, which is characterized in that in step 2, the addition of 3- amino benzocyclobutenes is the 1- alkene that step 1 is added
The 50~200% of propyl -2- cyanic acid ester group benzene quality.
Preferably, which is characterized in that in step 2, the 3- amino benzocyclobutene of addition and bismaleimide monomer
Mass ratio is 1：(1.5~2.5).
A kind of modified bismaleimide resin suitable for resin transfer molding is obtained using any of the above-described preparation method
It arrives, modified bismaleimide resin is presented viscose shape at room temperature, and 150~600cP, volatile matter are maintained in viscosity 6h at 90 DEG C
Less than 1.5%；Cure peak value corresponding temperature and be less than 225 DEG C, glass transition temperature is higher than 330 DEG C after solidification；Enhanced by glass cloth
The composite material that the modified bismaleimide resin obtains, dielectric constant is less than 3.8 under 10GHz, and dielectric loss is less than
0.01。
Compared with prior art, the present invention has technique effect beneficial below：
Present invention introduces two kinds of modifying agent to carry out modified bismaleimide monomer (BMI), both modifying agent are respectively 1-
Allyl -2- cyanic acid ester group benzene (ACB) and 3- amino benzocyclobutene (ABCB), ACB contain active group allyl and cyanic acid
Ester group, and ABCB contains amino and benzocyclobutene structure.Under pre-polymerization condition, allyl, amino can respectively with bismaleimide
Double bond the addition of ene alkene and Michael addition reactions occurs, and cyanic acid ester group, benzocyclobutene structural response activity are relatively
It is weak, it needs to participate in reacting at higher temperatures.This to contain ACB-BMI, ACB-BMI- in prepolymerization system structure
Multiplexed combination state is presented, compared with single in a variety of reaction products such as ACB, ACB-BMI-ABCB, ABCB-BMI, ABCB-BMI-ABCB
Modification mode more efficiently breaks the ordered structure of original bismaleimide monomer, reduces its crystallinity, molten to reduce
Point.Gained prepolymerization system crystallinity is low, and average molecular weight is relatively low, to which prepolymerization system can keep lower melting viscosity, together
Its dissolubility of Shi Gaishan.These have significant actively work for improving the processing technology of prepolymerization system, being adapted to RTM techniques
With.In addition, the cyanic acid ester group of performed polymer remaining, benzocyclobutene structure, bismaleimide ring are highly stable at normal temperatures, no
It can chemically react, this allows prepolymerization system to obtain longer storage period.When in use, prepolymerization system heat effect
Lower solidification, generally 160~200 DEG C can induce the chemical reaction of prepolymerization system, include bismaleimide remaining double bond oneself
The copolymerization of poly-, the autohemagglutination of the autohemagglutination of cyanic acid ester group, benzocyclobutene, bismaleimide double bond and benzocyclobutene, span come
Acid imide and copolymerization of cyanic acid ester group etc. are reacted, and prepolymerization system ultimately forms the network structure of high crosslink density, to show
Excellent heat resistance, and there is preferable toughness.In addition, cyclotrimerization can occur under heat effect for cyanate, triazine is generated
Ring structure so that curing system has lower dielectric constant and dielectric loss, and the dielectric properties of cyanate ester resin are in thermosetting property
It puts up the best performance in resin material, better than epoxy resin, bimaleimide resin even polyimide resin；Similarly, benzene
And cyclobutane resinoid also has excellent electric property, dielectric constant is small, and dielectric loss is low, constantly expands in electric field
Exhibition application.The present invention introduces cyanic acid ester group and benzocyclobutene structure simultaneously in resin prepolymer system, for ensureing span
The dielectric properties for further improving prepolymerization system while carrying out acid imide excellent heat resistance itself have very positive and effective work
With.One pot of two-step method is used when the present invention synthesizes, synthesis technology is easy, and three-waste free discharge is easy to industrialize.Gained is modified span
Bismaleimide resin is the performed polymer of modifying agent and bismaleimide monomer, is free of reactive diluent and solvent, and volatile matter is low.
Viscose shape is presented in the modified bismaleimide resin that the present invention is prepared at room temperature, and viscosity is low, is sticked at 90 DEG C
It is maintained at 150~600cP in degree 6h；The volatile matter tested at 150 DEG C is less than 1.5%；Solidification temperature is low, DSC tests (10 DEG C/
Min) show that initial cure temperature is less than 160 DEG C, solidification peak value corresponding temperature is less than 225 DEG C, and resin is at 200 DEG C when reality cures
At a temperature of keep 1~2h i.e. have some strength, can be demoulded, this shows that the resin processing techniques are excellent, be suitable for RTM works
Skill；Excellent heat resistance, DMA tests (5 DEG C/min, 1Hz) glass transition temperature Tg after the solidification of resin prepolymer system>330℃；Mechanical property
It can good, casting matrix bending strength 90MPa, bending modulus 4.0GPa.Cyanic acid ester group, benzo ring are introduced in prepolymerization system of the present invention
Butylene structure, dielectric properties are obviously improved.Using modified bismaleimide resin as matrix, prepared using glass cloth enhancing
Dielectric constant is less than 3.8 under composite material 10GHz, and dielectric loss is less than 0.01, shows excellent dielectric properties.
Description of the drawings
Fig. 1 is the DSC cure curve graph of modified bismaleimide resin of the present invention, wherein abscissa
Temperature indicates that temperature, ordinate Heat Flow indicate rate of heat flow.
Fig. 2 is the casting matrix DMA curve graphs of modified bismaleimide resin of the present invention, wherein abscissa
Temperature indicates that temperature, ordinate Storage Modulus indicate that storage modulus, ordinate Loss Modulus indicate
Loss modulus, ordinate Tan Delta indicate fissipation factor.
Specific implementation mode
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.
When actual implementation of the present invention, first by 1- allyl -2- cyanic acid ester group benzene and a part of bismaleimide monomer
Reaction a period of time, carry out first stage pre-polymerization；Then it is reduced to certain temperature, 3- amino benzocyclobutenes are added, is filled into another
The bismaleimide monomer of a part, is adjusted to preference temperature the reaction was continued that a period of time completes second stage pre-polymerization；Pass through
This pot of two-step method pre-polymerization, final cooling down obtain modified bismaleimide resin of the present invention.
High-temperature resistant low dielectric modified bismaleimide resin of the present invention suitable for RTM techniques, specifically can be by following step
It is rapid to prepare：
Step 1, the pre-polymerization of 1- allyl -2- cyanic acid ester group benzene and bismaleimide monomer；
1- allyl -2- cyanic acid ester group benzene is heated to 130~160 DEG C, bismaleimide is slowly added in 1 hour
Monomer, insulation reaction 1~3 hour, the two react to form homogeneous performed polymer through Diene-addition at this temperature；1- allyls-
The mass ratio of 2- cyanic acid ester group benzene and bismaleimide monomer is 1：(1.5~2.5), preferably 1:2；
The bismaleimide monomer has following structure：
Wherein, R is-CH2-、-O-、-SO2Or-O-Ph-C (CH3)2-Ph-O-；
Step 2, the pre-polymerization for the performed polymer that 3- amino benzocyclobutene is obtained with bismaleimide monomer and step 1；
Performed polymer obtained by step 1 is cooled down 20 DEG C or more, 3- amino benzocyclobutenes are added, readjusting temperature is
110~140 DEG C, bismaleimide monomer is slowly added in 1 hour, at this temperature insulation reaction 1~3 hour；3- ammonia
Base benzocyclobutene occurs Michael with performed polymer residual double bond obtained by step 1 and the bismaleimide monomer being newly added and adds
At reaction, the prepolymerization system of homogeneous phase transparent is formed, is cooled down up to the heat-resisting low dielectric modified bismaleimide tree of height suitable for RTM
Fat；
Wherein, 3- amino benzocyclobutene addition is the 1- allyl -2- cyanic acid ester group benzene quality that step 1 is added
50~200%, preferably 100%；The mass ratio for the bismaleimide monomer that 3- amino benzocyclobutene is added with this step is
1：(1.5~2.5), preferably 1:2；
Bismaleimide monomer described in this step has following structure, can be with the bismaleimide monomer of step 1
It is identical or different：
Wherein, R is-CH2-、-O-、-SO2Or-O-Ph-C (CH3)2-Ph-O-。
The present invention develops a kind of preparation method of the novel modified bismaleimide resin suitable for RTM techniques, draws
Enter two kinds of 1- allyl -2- cyanic acid ester groups benzene, 3- amino benzocyclobutene modifier modification bismaleimide monomers, they are total
With feature respectively contained there are two active group in molecular structure, wherein active group allyl and amino can be with bismaleimide
The double bond of monomer is reacted at a lower temperature, and another active group cyanic acid ester group and benzocyclobutene need to be increased to it is at higher temperature
Degree could participate in reaction；Polynary state is presented in the prepolymerization system obtained after pre-polymerization, breaks the regular of bismaleimide monomer
Structure reduces crystallinity, effectively reduces resin melt temperature, and can effectively prevent the precipitation of bismaleimide monomer.
Gained performed polymer molecular weight is low, and crystallinity is low so that prepolymerization system can keep low for a long time at processing temperatures
Viscous state.It is maintained at 150~600cP in viscosity 6h at 90 DEG C of prepolymerization system of actual measurement, suitable for the development of RTM moulding process.
Resin prepolymer system solidification temperature is low, and curing activity is high, and DSC shows that curing initiation temperature is less than 170 DEG C, cures peak
It is worth corresponding temperature and is less than 225 DEG C, shows higher reactivity.The solidification 2h degrees of cross linking are more than 96% at 200 DEG C of actual measurement.
Remaining active group such as cyanic acid ester group, benzocyclobutene etc. needs just begin participating at relatively high temperatures after pre-polymerization
Reaction, can induce the chemical reaction of residual activity group by generally 160~200 DEG C, as bismaleimide remaining double bond from
The copolymerization of poly-, the autohemagglutination of the autohemagglutination of cyanic acid ester group, benzocyclobutene, bismaleimide double bond and benzocyclobutene, span come
Acid imide and copolymerization of cyanic acid ester group etc. are reacted, high by standard cure system solidification post-crosslinking degree, form the net of high crosslink density
Network structure, to show excellent heat resistance, DMA tests curing system glass transition temperature and is higher than 330 DEG C.
The resin prepolymer system that the present invention obtains：Viscose shape is presented at room temperature, it is maintained at 150 at 90 DEG C in viscosity 6h~
600cP, volatile matter are less than 1.5%, can be heating and curing under 200 DEG C of temperature conditions.Process industrial art performance is excellent, meet RTM at
Requirement of the type technique for resin；Cured according to 150 DEG C/1h → 180 DEG C/1h → 200 DEG C/2h curing cycles, and 230
After curing 2h at DEG C, curing system glass transition temperature is more than 330 DEG C, and heat resistance is good.Glass cloth enhances the compound of the resin
Material, resin content 40% therein, composite material dielectric constant at 10GHz are less than 3.8, and dielectric loss is less than 0.01, far
Less than epoxy group and the test result of general bismaleimide resin based composites, excellent dielectric properties are shown.Use the resin
The composite materials property of preparation is excellent.
Specific embodiment is as follows.
Embodiment 1
In the 500ml vials equipped with thermometer, charging hopper and mechanical stirring device, the 1- allyls-of 50g are added
2- cyanic acid ester group benzene, is warming up to 140 DEG C, and 4, the 4 '-bismaleimide diphenyl-methanes of 100g are added in 1 hour, and continues
Insulation reaction 1 hour at 140 DEG C, system is in homogeneous phase transparent state at this time.System is cooled to 120 DEG C, and the 3- amino of 50g is added
Benzocyclobutene readjusts system temperature to 120 DEG C, 4, the 4 '-bismaleimide hexichol first of 100g is added in 1 hour
Alkane, and continue insulation reaction 1 hour at 120 DEG C.Cooling obtains the modified bismaleimide resin of rufous homogeneous phase transparent.
Embodiment 2
In the 500ml vials equipped with thermometer, charging hopper and mechanical stirring device, the 1- allyls-of 30g are added
2- cyanic acid ester group benzene, is warming up to 140 DEG C, 4, the 4 '-bismaleimide diphenyl-methanes of 75g is added in 1 hour, and continue
Insulation reaction 1 hour at 140 DEG C, system is in homogeneous phase transparent state at this time.System is cooled to 120 DEG C, and the 3- aminobenzenes of 60g are added
And cyclobutane, system temperature is readjusted to 120 DEG C, and 4, the 4 '-bismaleimide hexichol first of 120g are added in 1 hour
Alkane, and continue insulation reaction 1 hour at 120 DEG C.Cooling obtains the modified bismaleimide resin of rufous homogeneous phase transparent.
Embodiment 3
In the 500ml vials equipped with thermometer, charging hopper and mechanical stirring device, the 1- allyls-of 60g are added
2- cyanic acid ester group benzene, is warming up to 140 DEG C, and 4, the 4 '-bismaleimide diphenyl-methanes of 120g are added in 1 hour, and continues
Insulation reaction 1 hour at 140 DEG C, system is in homogeneous phase transparent state at this time.System is cooled to 120 DEG C, and the 3- amino of 30g is added
Benzocyclobutene readjusts system temperature to 120 DEG C, 4, the 4 '-bismaleimide hexichol first of 45g is added in 1 hour
Alkane, and continue insulation reaction 1 hour at 120 DEG C.Cooling obtains the modified bismaleimide resin of rufous homogeneous phase transparent.
Embodiment 4
In the 500ml vials equipped with thermometer, charging hopper and mechanical stirring device, the 1- allyls-of 50g are added
2- cyanic acid ester group benzene, is warming up to 130 DEG C, and 2,2 '-bis- [4- (4- maleimide phenoxyls) of 125g are added in 1 hour
Phenyl] propane, and continue insulation reaction 3 hours at 130 DEG C, system is in homogeneous phase transparent state at this time.System is cooled to 110
DEG C, the 3- amino benzocyclobutenes of 50g are added, readjusts system temperature to 110 DEG C, 2, the 2 '-of 125g is added in 1 hour
Bis- [4- (4- maleimide phenoxyls) phenyl] propane, and continue insulation reaction 3 hours at 110 DEG C.Cooling obtains red
The transparent modified bismaleimide resin of brown homogenous.
Embodiment 5
In the 500ml vials equipped with thermometer, charging hopper and mechanical stirring device, the 1- allyls-of 50g are added
2- cyanic acid ester group benzene, is warming up to 135 DEG C, 4, the 4 '-bismaleimide diphenyl ether of 100g is added in 1 hour, and continue
Insulation reaction 2 hours at 135 DEG C, system is in homogeneous phase transparent state at this time.System is cooled to 115 DEG C, and the 3- aminobenzenes of 50g are added
And cyclobutane, system temperature is readjusted to 115 DEG C, and 4, the 4 '-bismaleimide diphenyl ether of 100g are added simultaneously in 1 hour
Continue insulation reaction 2 hours at 115 DEG C.Cooling obtains the modified bismaleimide resin of rufous homogeneous phase transparent.
Embodiment 6
In the 500ml vials equipped with thermometer, charging hopper and mechanical stirring device, the 1- allyls-of 50g are added
2- cyanic acid ester group benzene, is warming up to 140 DEG C, and 4, the 4 '-bismaleimide diphenyl-methanes of 100g are added in 1 hour, and continues
Insulation reaction 1 hour at 140 DEG C, system is in homogeneous phase transparent state at this time.System is cooled to 115 DEG C, and the 3- amino of 50g is added
Benzocyclobutene readjusts system temperature to 115 DEG C, 4, the 4 '-bismaleimide diphenyl ether of 100g is added in 1 hour
And continue insulation reaction 2 hours at 115 DEG C.Cooling obtains the modified bismaleimide resin of rufous homogeneous phase transparent.
Embodiment 7
In the 500ml vials equipped with thermometer, charging hopper and mechanical stirring device, the 1- allyls-of 50g are added
2- cyanic acid ester group benzene, is warming up to 160 DEG C, 4, the 4 '-bismaleimide diphenyl sulphone (DPS)s of 100g is added in 1 hour, and continue
Insulation reaction 1 hour at 160 DEG C, system is in homogeneous phase transparent state at this time.System is cooled to 140 DEG C, and the 3- aminobenzenes of 50g are added
And cyclobutane, system temperature is readjusted to 140 DEG C, and 4, the 4 '-bismaleimide hexichol first of 100g are added in 1 hour
Alkane, and continue insulation reaction 1 hour at 140 DEG C.Cooling obtains the modified bismaleimide resin of rufous homogeneous phase transparent.
Embodiment 8
In the 500ml vials equipped with thermometer, charging hopper and mechanical stirring device, the 1- allyls-of 30g are added
2- cyanic acid ester group benzene, is warming up to 150 DEG C, 4, the 4 '-bismaleimide diphenyl sulphone (DPS)s of 45g is added in 1 hour, and continue
Insulation reaction 3 hours at 150 DEG C, system is in homogeneous phase transparent state at this time.System is cooled to 130 DEG C, and the 3- aminobenzenes of 60g are added
And cyclobutane, system temperature is readjusted to 130 DEG C, and 4, the 4 '-bismaleimide diphenyl sulphone (DPS)s of 90g are added in 1 hour, and
Continue insulation reaction 1 hour at 130 DEG C.Cooling obtains the modified bismaleimide resin of rufous homogeneous phase transparent.
Following performance is tested with the modified bismaleimide resin that embodiment 1 is prepared.
It is 250cP with rotational viscometer test modified bismaleimide resin viscosity at 90 DEG C, viscosity goes up after 6h
To 480cP.
Modified bismaleimide resin keeps 1h in 150 DEG C of baking ovens, measures volatile matter content 1.22%.
The curing activity of gained resin is characterized with differential scanning calorimeter, warm journey RT~350 DEG C, temperature rise rate 10
℃/min.As shown in Figure 1, modified bismaleimide resin curing initiation temperature is only 152 DEG C, and peak value corresponding temperature is 223
DEG C, show higher activity of curing reaction.
Using 150 DEG C/1h → 180 DEG C/1h → 200 DEG C/2h → 230 DEG C/2h systems solidification, it is fine and close that brownish black is obtained after solidification
Casting resin.Using dynamic thermomechanical analysis apparatus test curing system glass transition temperature, 5 DEG C of temperature rise rate/
min.As shown in Figure 2, storage modulus just starts substantially to decay at 330 DEG C or more, and losstangenttanδ peak value corresponding temperature is
Glass transition temperature is 382 DEG C.Test result shows that material has excellent heat resistance, can require to be higher than to temperature classification
300 DEG C of application field extends.
Using the resin as matrix, it is compound to be that reinforcing material is prepared using RTM techniques with E-glass cloth (specification 7628)
Plate of material, resin content are about 40%.Dielectric properties test is carried out under 10GHz, it is 3.7 to measure composite panel dielectric constant,
Dielectric loss angle tangent value is 0.008.It is much better than using epoxy and general bismaleimide resin as the similar composite material of matrix.
Claims (9)
1. a kind of preparation method of modified bismaleimide resin suitable for resin transfer molding, which is characterized in that packet
Include following steps,
1- allyl -2- cyanic acid ester group benzene is heated to 130~160 DEG C by step 1, and bismaleimide monomer, heat preservation is added
It is reacted, obtains homogeneous performed polymer；
3- amino benzocyclobutenes are added in the performed polymer obtained to step 1 for step 2, and it is 110~140 DEG C to adjust temperature, is added
Enter bismaleimide monomer, heat preservation is reacted, and the modified bismaleimide tree suitable for resin transfer molding is obtained
Fat.
2. the preparation side of the modified bismaleimide resin according to claim 1 suitable for resin transfer molding
Method, which is characterized in that in step 1,1- allyl -2- cyanic acid ester group benzene is heated to 130~160 DEG C, in 1 hour slowly
Bismaleimide monomer is added, insulation reaction 1~3 hour, obtains homogeneous performed polymer at this temperature.
3. the preparation side of the modified bismaleimide resin according to claim 1 suitable for resin transfer molding
Method, which is characterized in that in step 1, the mass ratio of 1- allyl -2- cyanic acid ester group benzene and bismaleimide monomer is 1：
(1.5~2.5).
4. the preparation side of the modified bismaleimide resin according to claim 1 suitable for resin transfer molding
Method, which is characterized in that in step 1, bismaleimide monomer has following structure,
Wherein, R is-CH2-、-O-、-SO2Or-O-Ph-C (CH3)2-Ph-O-。
5. the preparation side of the modified bismaleimide resin according to claim 1 suitable for resin transfer molding
Method, which is characterized in that in step 2, the performed polymer that step 1 is obtained cools down 20 DEG C or more, and 3- amino benzocyclobutenes are added,
It is 110~140 DEG C to adjust temperature, bismaleimide monomer is slowly added in 1 hour, at this temperature insulation reaction 1~3
Hour, obtain the modified bismaleimide resin suitable for resin transfer molding.
6. the preparation side of the modified bismaleimide resin according to claim 1 suitable for resin transfer molding
Method, which is characterized in that in step 2, bismaleimide monomer has following structure,
Wherein, R is-CH2-、-O-、-SO2Or-O-Ph-C (CH3)2-Ph-O-。
7. the preparation side of the modified bismaleimide resin according to claim 1 suitable for resin transfer molding
Method, which is characterized in that in step 2, the addition of 3- amino benzocyclobutenes is the 1- allyl -2- cyanic acid that step 1 is added
The 50~200% of ester group benzene quality.
8. the preparation side of the modified bismaleimide resin according to claim 1 suitable for resin transfer molding
Method, which is characterized in that in step 2, the 3- amino benzocyclobutene of addition and the mass ratio of bismaleimide monomer are 1：
(1.5~2.5).
9. a kind of modified bismaleimide resin suitable for resin transfer molding, which is characterized in that use claim 1
~8 any one of them preparation methods obtain, and modified bismaleimide resin is presented viscose shape at room temperature, viscosity 6h at 90 DEG C
It is inside maintained at 150~600cP, volatile matter is less than 1.5%；Cure peak value corresponding temperature and is less than 225 DEG C, glass transition temperature after solidification
Higher than 330 DEG C；Enhance the composite material that the modified bismaleimide resin obtains by glass cloth, dielectric is normal under 10GHz
Number is less than 3.8, and dielectric loss is less than 0.01.
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| CN1465212A (en) * | 2000-09-07 | 2003-12-31 | 奥克-三井有限公司 | Manufacturing fire retardant circuit boards without the use of fire retardant resin additives |
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