CN106221212B - A kind of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling and preparation method thereof - Google Patents
A kind of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling and preparation method thereof Download PDFInfo
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Abstract
Aligned carbon nanotube beam/thermosetting resin the present invention relates to a kind of filling of polyphenylene oxide and preparation method thereof.Aligned carbon nanotube beam (ACNTB) particle that polyphenylene oxide (PPO) is filled is added in cyanate (CE) resin system, it is cured to obtain a kind of high-performance CE composite systems.In carbon pipe and carbon ligament that PPO is filled in ACNTB by the present invention, increase ACNTB mechanical properties, and the PPO ACNTB particles filled are added in CE resins, after cured processing, a kind of high performance CE resin systems composite material is obtained, with excellent mechanical property, heat resistance, flame retardant property etc..The preparation method of the present invention has the characteristics that applicability is wide, operating procedure is simple, and the resin system of preparation can be used for preparing aerospace high-performance composite materials, electronic device etc..
Description
Technical field
The invention belongs to field of high polymer composite material preparation, and in particular to a kind of orientation carbon of high-performance polyphenylene oxide filling
Nanotube bundle/thermosetting resin and preparation method thereof.
Technical background
Cyanate（CE）Resin has high hot property, excellent mechanical property as a kind of high performance resin, solidfied material
Energy, low dielectric properties etc., in electronic manufacture, field of aerospace is widely used.But due to CE resin cured matters
Middle triazine ring structure high degree of symmetry, crystallinity are high so that the brittleness of resin cured matter is larger, it is therefore desirable to carry out toughening and change.This
Outside, the harshness of high-tech development and material application environment, it is desirable that CE composite materials have more and more excellent comprehensive performance.Cause
This, actively improves the performance of CE resin systems, for its application field range is promoted to have positive effect.At present, for CE trees
The study on the modification method of fat mainly has：Inorganic particulate such as carbon nanotube, Nano particles of silicon dioxide, clay, whisker etc. are modified CE；
Thermosetting resin such as epoxy resin, bimaleimide resin etc. are modified CE；Thermoplastic resin such as polysulfones, polyether sulfone, polyethers acyl
Imines etc. is modified CE；The modified CE resins of rubber elastomer such as liquid end carboxyl nitrile rubber, butadiene-styrene rubber etc. and synthesizing new knot
CE systems of structure etc..Result of study shows using inoganic particle modified CE to its comprehensive performance（It is hot property, mechanical property, fire-retardant
Performance etc.）Improving has good effect.
Aligned carbon nanotube beam（ACNTB）It is the carbon nano-tube bundle of a large amount of carbon nano-tube oriented arrangements, it is collection mechanical property, soft
The one such as toughness, Large strain failure, high conduction performance, excellent optical transmittance in strain transducer, field emmision material, surpasses
The fields such as grade capacitor, resonance control have potential application value.But since there are a large amount of holes between carbon nanotube and pipe
Gap, pipe intermolecular forces are weak so that carbon nanotube cannot effectively transmit load, lead to the mechanical property of carbon nano-tube bundle far below single
The mechanical property of root carbon pipe.Therefore, the mechanical property of aligned carbon nanotube beam how is improved for promoting aligned carbon nanotube beam
Application have positive effect；Simultaneously on the basis of mechanical property is improved, it is also necessary to not damage heat resistance, the combustion of original material
Burn the other performances such as performance.
Invention content
In order to overcome CE resins itself brittleness shortcoming and solve its high heat-resisting and high-tensile strength faced in high-tech area application
It learns performance etc. and requires problem, the present invention provides a kind of high-performance polyphenylene oxide（PPO）The ACNTB of filling（ACNTB@PPO）/ thermosetting
Property resin and preparation method thereof, the resin system of preparation can be used for preparing high-speed figure and high frequency printed circuit board, aviation boat
Its high performance structures composite material etc..
In order to achieve the above object, the technical solution adopted in the present invention is：A kind of aligned carbon nanotube beam of polyphenylene oxide filling/
Thermosetting resin and preparation method thereof includes the following steps：
The mixture of cyanate ester resin or cyanate ester resin and catalyst is heated into 0.5 ~ 1.5h at 130 ~ 150 DEG C, so
The aligned carbon nanotube bundle of particle of bismaleimide and polyphenylene oxide filling is added in afterwards, then at 140 ~ 150 DEG C of 1 ~ 1.5h of heating, is obtained
To prepolymerization system；Then prepolymerization system is injected in preheated mold, is carried out at curing after vacuum defoamation at 150 ~ 160 DEG C
It manages, aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling is obtained after natural cooling；
The aligned carbon nanotube bundle of particle of the polyphenylene oxide filling（Abbreviation ACNTB@PPO）Preparation method include following step
Suddenly：Polyphenylene oxide PPO is dissolved in benzene kind solvent, then addition aligned carbon nanotube beam ACNTB, vacuum defoamation under room temperature；Then
Alcohols solvent is added in, stirs 1.5 ~ 2.5h, is then filtered, dry cake obtains the aligned carbon nanotube beam of polyphenylene oxide filling
ACNTB@PPO particles.
In above-mentioned technical proposal, cyanate ester resin, bismaleimide, catalyst, polyphenylene oxide filling orientation carbon nanometer
Tube bank（ACNTB@PPO）The mass ratio of particle is 100:（3~10）∶（0~1）∶（1~4）；The polyphenylene oxide（PPO）, benzene kind solvent,
Aligned carbon nanotube beam（ACNTB）, alcohols solvent mass ratio be（2~5）∶（90~100）∶（1~2）∶200.
In above-mentioned technical proposal, ACNTB is added in into the benzene class solution of PPO, stirring vacuum deaeration under room temperature, in vacuum pressure
Under power, the solution of PPO can be effectively penetrated into the pipe and ligament of ACNTB, and as solvent volatilizees, solution becomes viscous（5~20Pa·
s）, alcohol is added in, ACNTB PPO particle powders are obtained after filtering solution and drying after stirring；In acquired ACNTB@PPO particles
PPO contents are about 40 ~ 75wt%.Benzene kind solvent can be toluene, and alcohols solvent can be ethyl alcohol.
In above-mentioned technical proposal, in order to be effectively increased contents of the PPO in ACNTB, suitable control is needed containing ACNTB's
PPO benzene kind solvent viscosity, solution viscosity is too dilute, and contents of the PPO in ACNTB can be caused to reduce, and solution viscosity is too high unfavorable
With the decentralized processings of ACNTB@PPO in subsequent processing.Solution viscosity is controlled can fully ensure that PPO has in 5 ~ 20Pas
Effect is filled in ACNTB and particle later stage decentralized processing.Ethyl alcohol is added in during ACNTB@PPO particles are prepared, due to PPO
Insoluble in ethyl alcohol, benzene kind solvent is soluble in alcohols, and therefore, the addition of alcohols solvent is in addition to can effectively disperse
ACNTB PPO particles can also extract benzene kind solvent, reduce benzene kind solvent content in ACNTB PPO particles, be effectively retained PPO
Loading in ACNTB.
In above-mentioned technical proposal, the polyphenylene oxide is the polyphenylene oxide that the number-average molecular weight of ethenyl blocking is 1100 ~ 2200；
The ACNTB is orientation multi-wall carbon nanometer tube bundle, and ACNTB not only has excellent heat resistance, and carbon nanotube microscopic orientation, can
Ensure that the ACNTB after filling has excellent mechanical property etc..The temperature of initial decomposition of the ACNTB is more than 661 DEG C；The cyanogen
Acid ester resin is dicyclopentadiene bisphenol type cyanate ester resin, bisphenol-A type cyanate ester resin, Bisphenol F type cyanate ester resin, double
One or several kinds in phenol E types cyanate ester resin, Novolac Cyanate Ester Resins；The bismaleimide is 4,4'- methylenes
Base two（N-phenylmaleimide）、N,N'-（4- methyl-1s, 3- phenylenes）Bismaleimide, diphenyl ether bismaleimide
One or several kinds in amine；The catalyst is 4,4' diaminodiphenyl sulfone, 4,4'- diaminodiphenylmethane, tin dilaurate
One or several kinds in dibutyl tin, Dibutyltin oxide, imidazoles, triethylamine, nonyl phenol, dibutyl tin laurate.
In above-mentioned technical proposal, the curing process condition is 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h.
The invention also discloses the aligned carbon nanotube beam/heat of a kind of polyphenylene oxide filling obtained by above-mentioned preparation method
Thermosetting resin.
The present invention further discloses a kind of preparation methods of ACNTB particles, include the following steps：PPO is dissolved in benzene class
In solvent, ACNTB is then added in, vacuum defoamation under room temperature；Then alcohols solvent is added in, stirs 1.5 ~ 2.5h, then filters, is dry
Dry filter cake obtains the aligned carbon nanotube of polyphenylene oxide filling（ACNTB@PPO）Particle.The PPO, benzene kind solvent, ACNTB, alcohols
The mass ratio of solvent is（2~5）∶（90~100）∶（1~2）∶200；Vacuum defoamation to system viscosity is 5 ~ 20Pas under room temperature；So
After add in alcohols solvent.
The PPO polyphenylene oxide of low molecular weight is filled between aligned carbon nanotube beam ACNTB pipes and pipe by the present invention can in gap
To improve the specific strength of ACNTB carbon nano-tube bundles, it may modify the mechanical property of material, while material other performance can be kept for example excellent
Different heat resistance, electrical property etc..The ACNTB filled using the PPO polyphenylene oxide with functionalized end groups is come modified cyanic acid ester（CE）
Resin, the ACNTB of the PPO polyphenylene oxide filling of this functionalized end groups can have strong interface interaction power with CE resin matrixes,
Mechanical property, hot property of CE resins etc. can be effectively improved, the CE resin systems of excellent combination property are obtained, available for producing
High-speed figure and high frequency printed circuit board, aerospace high performance structures composite material etc..
Compared with prior art, the beneficial effects of the invention are as follows：
（1）The present invention is modified and cyanate/bis- for the first time using the ACNTB that the polyphenylene oxide PPO with functionalized end groups is filled
Horse copolymerization system can be reacted since the polyphenylene oxide of functionalization contains with bimaleimide resin, and bimaleimide resin
Can with CE resin reactions, therefore polyphenylene oxide filling aligned carbon nanotube beam（ACNTB@PPO）Particle can be effectively dispersed in resinite
In system and its interface with resin matrix has strong interface interaction power；Especially it is that of avoiding thermoplastic polyphenylene ethers and thermosetting property cyanogen
The problem of acid esters system is incompatible, the performance to improve composite material provide good basis.
（2）High heat-resisting and high tenacity PPO is filled in ACNTB by the present invention using the mode of vacuum infiltration for the first time, is increased
Add the two interfacial effect, can not only effectively reduce the defects of ACNTB, greatly improve the effect between carbon pipe, effectively improve
The mechanical property advantage of ACNTB can also improve the toughness of ACNTB；Other performance advantages of ACNTB are kept simultaneously.
（3）CE resin systems prepared by the present invention have excellent mechanical property, heat resistance and high flame resistance etc.；
The aligned carbon nanotube bundle of particle filled especially with polyphenylene oxide is modified, than directly utilizing polyphenylene oxide and orientation carbon nanometer
Two kinds of substances of tube bank obtain superior performance, and bending strength can reach 242MPa, achieve unexpected technique effect.
Description of the drawings
Fig. 1 is the scanning electron microscope of ACNTB and ACNTB@PPO particles（SEM）And transmission electron microscope（TEM）Figure；
Fig. 2 is the surface sweeping electron microscope of the section after the test of 1 material fracture toughness of embodiment；
Fig. 3 is the section SEM after the test of ACNTB@PPO/CE and ACNTB/PPO/CE material fracture toughness in embodiment 2
Figure.
Specific embodiment
Embodiment 1
（1）The preparation of ACNTB@PPO
The PPO of the number-average molecular weight 2200 of 2g ethenyl blockings is dissolved in about 90g toluene solutions, obtains PPO solution,
The ACNTB of 1.5g is added in solution, stirs vacuum defoamation under room temperature, under capillary force and vacuum pressure, PPO solution meetings
It penetrates between ACNTB pipes and pipe in hole, as solvent volatilizees, after solution becomes viscous（5Pa·s）, 200g ethyl alcohol is added in, stirs 2h
The aligned carbon nanotube bundle of particle of polyphenylene oxide filling is obtained by suction filtration solution and after drying, is denoted as ACNTB@PPO particle powders,
PPO contents are about 51wt% in acquired ACNTB@PPO particles.Fig. 1 is the scanning electron microscope of ACNTB and ACNTB@PPO particles
（SEM）And transmission electron microscope（TEM）Picture, a ACNTB, b are ACNTB@PPO particles.Comparison diagram 1a and b, it can be seen that quilt
PPO filling ACNTB between carbon pipe and carbon pipe gap disappear, since PPO is filled in ACNTB voids, can strengthen carbon pipe it
Between effect, this, which allows for ACNTB, can excellent mechanical property, while have both the other excellent properties of carbon pipe such as hot property
Deng.
（2）It is prepared by ACNTB@PPO/CE composite materials
By 100gCE（Bisphenol A cyanate ester）Pre-polymerization stirring 1.5h is heated after being mixed with 1g diaminodiphenylsulfones at 145 DEG C,
Then 5gN, N'-4,4'- diphenyl methane dimaleimides and 1gACNTB@PPO particles are added in, then heats pre-polymerization at 145 DEG C and stirs
1h is mixed, obtains ACNTB@PPO/CE prepolymerization systems；In the mold that prepolymerization system injection is preheated through 145 DEG C, at 150-160 DEG C
After vacuum defoamation, curing process is carried out according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h of temperature program(me), it is natural
Aligned carbon nanotube beam/thermosetting resin of ACNTB@PPO/CE composite systems, i.e. polyphenylene oxide filling is obtained after cooling.
For contrast properties, it is prepared for being not added with the CE resin system materials of ACNTB@PPO using identical curing process.
Table 1 lists the mechanical properties of ACNTB PPO/CE composite systems, glass transition temperature and has limited oxygen index.From table
As can be seen that the mechanical property for adding in the resin system of ACNTB@PPO is apparently higher than the CE resin systems for not adding ACNTB@PPO,
The hot property and flame resistance for adding in the resin system of ACNTB@PPO can be also superior to the CE resin systems for not adding ACNTB@PPO.Figure
The 2 surface sweeping Electronic Speculum for the section after material fracture toughness test（SEM）Photo.From figure 2 it can be seen that ACNTB@PPO/CE materials
The section of material（Fig. 2 b）It is coarse compared with the CE sections for being not added with ACNTB@PPO particles（Fig. 2 a）, and ACNTB PPO particles have crackle
There are apparent passivation and inhibiting effect, it means that the mechanical property for adding in the resin system of ACNTB@PPO is better than not adding
The CE resin systems of ACNTB@PPO.
The mechanical properties of 1 ACNTB PPO/CE composite systems of table, glass transition temperature and there is limited oxygen index
| Performance | ACNTB@PPO/CE | CE |
| Bending strength/MPa | 201 | 140 |
| Fracture toughness/MPam1/2 | 1.09 | 0.75 |
| Glass transition temperature（Tg）/℃ | 296 | 292 |
| There is limited oxygen index | 27 | 26 |
Embodiment 2
By 50gCE（Bisphenol A cyanate ester）With will 0.5g diaminodiphenylsulfones mix after 145 DEG C heat pre-polymerizations stirring
Then 1.5h adds in 1gACNTB@PPO prepared in 2.5gN, N'-4,4 '-diphenyl methane dimaleimide and embodiment 1
Son, then pre-polymerization stirring 1h is heated at 145 DEG C, obtain ACNTB@PPO/CE prepolymerization systems；By prepolymerization system injection through 145 DEG C of preheatings
Mold in, at 150-160 DEG C after vacuum defoamation, according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 of temperature program(me)
DEG C/2h carries out curing process, ACNTB@PPO/CE composite systems are obtained after natural cooling.
For contrast properties, prepared using identical curing process and be equal to content with ACNTB@PPO/CE composite materials
The CE resin composite materials of ACNTB and PPO（ACNTB/PPO/CE）.Table 2 lists ACNTB@PPO/CE composite systems
Mechanical property, glass transition temperature and there is limited oxygen index.In contrast table 1 not plus the CE systems of ACNTB PPO/CE, can be with
Mechanical property, hot property and the flame resistance of ACNTB@PPO/CE systems prepared in discovery table 2 can have apparent advantage, with
Compared with the ACNTB/PPO/CE composite materials of PPO, the performance of ACNTB@PPO/CE systems also has the ACNTB of the equivalent content of addition
Have apparent advantage, reason is that the PPO in ACNTB@PPO can be reacted with resin system, can be effectively improved ACNTB particles with
The interface interaction and dispersibility of resin matrix.After Fig. 3 is the test of ACNTB@PPO/CE and ACNTB/PPO/CE material fracture toughness
Section SEM photograph.From figure 3, it can be seen that ACNTB@PPO/CE（Fig. 3 a）With ACNTB/PPO/CE materials（Fig. 3 b）Middle carbon
Pipe fracture is significantly different compared with mode, and in ACNTB@PPO/CE materials, the fracture of carbon pipe is irregular, and ACNTB/PPO/CE materials
Face face stacked form is presented in the fracture of middle carbon pipe, it is meant that the carbon Guan Gengneng of ACNTB PPO effectively transmits power load, so as to more can
Effectively improve the mechanical property of material.
The mechanical properties of 2 ACNTB PPO/CE composite systems of table, glass transition temperature and there is limited oxygen index
| Performance | ACNTB@PPO/CE | ACNTB/PPO/CE |
| Bending strength/MPa | 242 | 212 |
| Fracture toughness/MPam1/2 | 1.29 | 1.06 |
| Glass transition temperature/DEG C | 297 | 294 |
| There is limited oxygen index | 27.5 | 27.1 |
Embodiment 3
（1）The preparation of ACNTB@PPO
It calculates by weight, the PPO of the number-average molecular weight 1100 of 2g ethenyl blockings is dissolved in about 90g toluene solutions, is obtained
To the toluene solution of PPO, 2gACNTB is added in the solution, stirring vacuum deaeration under room temperature, under the vacuum pressures, the toluene of PPO
Solution can be effectively penetrated between ACNTB pipes in hole, and as solvent volatilizees, solution becomes viscous（20Pa·s）, add in about 200g second
Alcohol obtains ACNTB PPO particle powders after stirring 2h after filtering solution and drying.PPO contains in acquired ACNTB@PPO particles
Amount is about 40wt%.
（2）It is prepared by ACNTB@PPO/CE composite materials
By 50gCE（Bis-phenol E type cyanates）Pre-polymerization stirring 2h is heated at 145 DEG C, then adds in 1.5gN, N'-4,4'- bis-
Phenylate bismaleimide and 2gACNTB@PPO particles, then pre-polymerization stirring 1h is heated at 145 DEG C, obtain ACNTB@PPO/CE pre-polymerizations
System；In the mold that prepolymerization system injection is preheated through 145 DEG C, at 150 ~ 160 DEG C after vacuum defoamation, according to temperature program(me)
160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h carries out curing process, and obtaining ACNTB@PPO/CE after natural cooling answers
Condensation material system.
For contrast properties, the CE materials for not adding ACNTB@PPO are prepared using identical curing process.Table 3 lists
The mechanical properties of ACNTB PPO/CE composite systems, glass transition temperature and there is limited oxygen index.From table it can be found that
The addition of ACNTB@PPO particles significantly improves the mechanical property, hot property and flame resistance energy of CE resin systems.
The mechanical properties of 3 ACNTB PPO/CE composite systems of table, glass transition temperature and there is limited oxygen index
| Performance | ACNTB@PPO/CE | Bisphenol E-type CE |
| Bending strength/MPa | 183 | 92 |
| Fracture toughness/MPam1/2 | 1.03 | 0.63 |
| Glass transition temperature/DEG C | 282 | 269 |
| There is limited oxygen index | 29 | 24.9 |
Embodiment 4
（1）The preparation of ACNTB@PPO
It calculates by weight, the PPO of the number-average molecular weight 1100 of 5g ethenyl blockings is dissolved in about 90g toluene solutions, is obtained
To the toluene solution of PPO, 1gACNTB is added in the solution, stirring vacuum deaeration under room temperature, under the vacuum pressures, the toluene of PPO
Solution can be effectively penetrated between ACNTB pipes in hole, and as solvent volatilizees, solution becomes viscous（10Pa·s）, add in about 200g second
Alcohol obtains ACNTB PPO particle powders after stirring 2h after filtering solution and drying.PPO contains in acquired ACNTB@PPO particles
Amount is about 75wt%.
（2）It is prepared by ACNTB@PPO/CE composite materials
By 50gCE（Novolac Cyanate Eater Resin）With will 0.0005g dibutyl tin laurates mix after 130 DEG C heat pre-polymerizations
0.5h is stirred, then adds in 5gN, N'- (4- methyl-1s, 3- phenylenes) bismaleimide and 1.5gACNTB@PPO particles, then
Pre-polymerization stirring 1h is heated at 145 DEG C, obtains ACNTB@PPO/CE prepolymerization systems；By mold of the prepolymerization system injection through 145 DEG C of preheatings
In, at 150 ~ 160 DEG C after vacuum defoamation, according to 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h of temperature program(me)
Curing process is carried out, ACNTB@PPO/CE composite systems are obtained after natural cooling.
For contrast properties, the CE materials for not adding ACNTB@PPO are prepared using identical curing process.Table 4 lists
The mechanical properties of ACNTB PPO/CE composite systems, glass transition temperature and there is limited oxygen index.From table it can be found that
The addition of ACNTB@PPO particles significantly improves the mechanical property, hot property and flame resistance energy of CE resin systems.
The mechanical properties of 4 ACNTB PPO/CE composite systems of table, glass transition temperature and there is limited oxygen index
| Performance | ACNTB@PPO/CE | Phenol aldehyde type CE |
| Bending strength/MPa | 173 | 81 |
| Fracture toughness/MPam1/2 | 1.23 | 0.79 |
| Glass transition temperature/DEG C | 346 | 343 |
| There is limited oxygen index | 31 | 29 |
Claims (7)
1. a kind of preparation method of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling, which is characterized in that including as follows
Step：
The mixture of cyanate ester resin or cyanate ester resin and catalyst is heated into 0.5 ~ 1.5h, Ran Houjia at 130 ~ 150 DEG C
Enter the aligned carbon nanotube bundle of particle of bismaleimide and polyphenylene oxide filling, then at 140 ~ 150 DEG C of 1 ~ 1.5h of heating, obtain pre-
Aggressiveness system；Then prepolymerization system is injected in preheated mold, carries out curing process after vacuum defoamation at 150 ~ 160 DEG C,
Aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling is obtained after natural cooling；
The preparation method of the aligned carbon nanotube bundle of particle of the polyphenylene oxide filling includes the following steps：Polyphenylene oxide is dissolved in benzene class
In solvent, aligned carbon nanotube beam is then added in, vacuum defoamation under room temperature；Then alcohols solvent is added in, stirs 1.5 ~ 2.5h, so
It filters afterwards, dry cake obtains the aligned carbon nanotube bundle of particle of polyphenylene oxide filling.
2. the preparation method of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling according to claim 1, feature
It is：The curing process condition is 160 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h.
3. the preparation method of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling according to claim 1, feature
It is：The polyphenylene oxide is the polyphenylene oxide that the number-average molecular weight of ethenyl blocking is 1100 ~ 2200；The aligned carbon nanotube beam
To be orientated multi-wall carbon nanometer tube bundle；The temperature of initial decomposition of the aligned carbon nanotube beam is more than 661 DEG C.
4. the preparation method of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling according to claim 1, feature
It is：The cyanate ester resin is dicyclopentadiene bisphenol type cyanate ester resin, bisphenol A cyanate ester resin, bisphenol-f type cyanic acid
One or several kinds in ester resin, bisphenol E-type cyanate resin, Novolac Cyanate Ester Resins；The bismaleimide is
4,4'- methylene two（N-phenylmaleimide）、N,N'-（4- methyl-1s, 3- phenylenes）Bismaleimide, diphenyl ether are double
One or several kinds in maleimide.
5. the preparation method of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling according to claim 1, feature
It is：The catalyst is 4,4' diaminodiphenyl sulfone, 4,4'- diaminodiphenylmethane, dibutyl tin laurate, two fourths
One or several kinds in base tin oxide, imidazoles, triethylamine, nonyl phenol, dibutyl tin laurate.
6. the preparation method of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling according to claim 1, feature
It is：The quality of aligned carbon nanotube bundle of particle that the cyanate ester resin, bismaleimide, catalyst, polyphenylene oxide are filled
Than being 100:（3~10）∶（0~1）∶（1~4）；The polyphenylene oxide, benzene kind solvent, aligned carbon nanotube beam, alcohols solvent quality
Than for（2~5）∶（90~100）∶（1~2）∶200.
7. the preparation method of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling according to claim 1, special
Sign is：When preparing the aligned carbon nanotube bundle of particle of polyphenylene oxide filling, vacuum defoamation to system viscosity is 5 ~ 20 under room temperature
Pa·s；Then alcohols solvent is added in.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810113257.6A CN108285642B (en) | 2016-07-28 | 2016-07-28 | Polyphenyl ether filled oriented carbon nanotube bundle/thermosetting resin |
| CN201610604641.7A CN106221212B (en) | 2016-07-28 | 2016-07-28 | A kind of aligned carbon nanotube beam/thermosetting resin of polyphenylene oxide filling and preparation method thereof |
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| CN103709748A (en) * | 2013-12-30 | 2014-04-09 | 苏州大学 | Self-repairing cyanate ester resin system and preparation method thereof |
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| CN104801245A (en) * | 2015-04-02 | 2015-07-29 | 苏州大学 | Epoxy resin filling aligned carbon nanotube bundle capsules and preparation method thereof |
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