CN106750297A - A kind of low dielectric bismaleimide resin system and preparation method thereof - Google Patents
A kind of low dielectric bismaleimide resin system and preparation method thereof Download PDFInfo
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- CN106750297A CN106750297A CN201611132719.6A CN201611132719A CN106750297A CN 106750297 A CN106750297 A CN 106750297A CN 201611132719 A CN201611132719 A CN 201611132719A CN 106750297 A CN106750297 A CN 106750297A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
- C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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
Abstract
The invention discloses a kind of low dielectric bismaleimide resin system and preparation method thereof, with BMI, allyl compound, mesoporous silicon oxide, polyphenylene oxide as raw material, by preparing the coating mesoporous silica of polyphenylene oxide, and bismaleimide resin system is applied it to, prepare low dielectric high-performance bismaleimide resin system；The features such as method disclosed by the invention has process is simple, applicability is wide, prepared material has a wide range of applications potentiality in Aeronautics and Astronautics and electronic applications.
Description
Technical field
The invention belongs to high-performance resin matrix technical field, it is related to a kind of low dielectric high performance resin based composites,
Specifically related to a kind of low dielectric bismaleimide resin system and preparation method thereof.
Background technology
Bismaleimide resin system is a kind of typical high-performance thermosetting resin, with excellent mechanical property,
Hot property and electrical property etc., it has prominent application potential in Aeronautics and Astronautics field of electronic materials.With microelectric technique
High speed development, the performance of existing bismaleimide resin system material can not meet high integration, more low-power consumption property high
The development of energy electronic product, this is accomplished by developing the more excellent low dielectric high-performance bismaleimide resin system of performance.
Using inorganic particulate to the bi-maleimide modified easy mechanical property and hot property for improving bimaleimide resin, but not
The dielectric properties of material can substantially be reduced.Mesoporous silicon oxide is a kind of inorganic material with pore structure, with great
Specific surface area, substantial amounts of Si~O~Si segments and abundant silicone hydroxyl, thus its be design have prominent mechanical property,
Heat resistance and dielectric properties（Dielectric constant about 1.5~1.7）Material provide advantage.Regrettably, although mesoporous two
The material of silica can be obviously improved the mechanical property even hot property of polymer matrix composites, but not send out fully
Its low-dielectric energy advantage is waved, its reason is that during material forming process, small-molecule substance can penetrate into silica
In mesoporous, so as to its low-dielectric energy cannot be made full use of.Further, since mesoporous silicon oxide has specific surface area high, its
The viscosity that can substantially increase resin system is added, causes resin forming manufacturability to be deteriorated.Therefore, how to mesoporous silicon oxide
It is mesoporous effectively to be sealed, and not appreciably affect under its low-dielectric energy and resin forming process conditions for promoting its low dielectric
Performance applications have positive effect.Polyphenylene oxide（PPO）It is a kind of important High performance plastic resin, it possesses glass higher
Change transition temperature（Tg=210℃）, good heat resistance and dimensional stability, toughness higher, relatively low hydroscopicity, although PPO
Addition can reduce the dielectric properties of aathermoset resin system to a certain extent, but, high level PPO is added and can be reduced tree
Crosslink density or other performance such as intensity of resin system and heat resistance etc., and PPO is used alone reduces thermosetting resin body
The dielectric properties effect of system is poor.
The content of the invention
It is an object of the invention to provide a kind of low dielectric bismaleimide resin system and preparation method thereof, will have
Mesoporous sealing of the material of low dielectric to mesoporous silicon oxide, is conducive to maintaining the low-dielectric energy of mesoporous silicon oxide, so that
Promote it in the application in development dielectric materials field.
In order to achieve the above object, the technical solution adopted by the present invention is：A kind of low dielectric bismaleimide resin
The preparation method of system, comprises the following steps：BMI and allyl compound are heated to clear solution, are subsequently adding
The coating mesoporous silicon dioxide granule of polyphenylene oxide, stirring obtains performed polymer；Then in performed polymer being poured into mould, in 130~150 DEG C
Vacuumize 30~40min；Then solidified at 150~230 DEG C of temperature, obtained low dielectric bismaleimide resin
System.
In above-mentioned technical scheme, raw material components and quality proportioning are 100 parts of BMI；Allyl compound 50
~100 parts；2~8 parts of the coating mesoporous silica of polyphenylene oxide.
In above-mentioned technical scheme, BMI and allyl compound are heated with stirring at 130~140 DEG C
Bright solution；Natural cooling obtains solidfied material and is low dielectric bismaleimide resin system after solidifying 7~9 hours.
In above-mentioned technical scheme, described BMI is dimaleoyl imino diphenyl-methane, span carrys out acyl
The methyl phenyl ethers anisole of imido grpup two.
In above-mentioned technical scheme, described allyl compound is diallyl bisphenol, diallyl bisphenol S, allyl
Base aralkyl phenol, polyallyl ether ketone, allyl phenol epoxy resin, N- pi-allyl arylamine.
In above-mentioned technical scheme, stir 30~50min in 130~150 DEG C and obtain performed polymer.
In above-mentioned technical scheme, the preparation method of the coating mesoporous silicon dioxide granule of polyphenylene oxide：Polyphenylene oxide is dissolved in benzene
In class solvent, mesoporous silicon oxide is added, is added after stirring in the aqueous solution containing surfactant, form oil-in-water system,
Stirring obtains the coating mesoporous silicon dioxide granule of polyphenylene oxide after 4~6 hours；The mass ratio of the polyphenylene oxide and mesoporous silicon oxide
For（1~3.3）∶1.
In above-mentioned technical scheme, the preferred toluene of benzene kind solvent, polyphenylene oxide is 1 with the mass ratio of benzene kind solvent:（10~
18）；Surfactant is neopelex, lauryl sodium sulfate, Monododecylphosphate potassium etc., contains surface
The mass concentration of surfactant is 0.1~0.3% in the aqueous solution of activating agent；Polyphenylene oxide is polyphenylene oxide resin, including different points
The polyphenylene oxide resin and its modified polyphenylene ether resin of son amount（Such as：Number-average molecular weight（Mn）It is 17300 polyphenylene oxide (PPO*
630), Mn is the polyphenylene oxide (PPO* MX9000-111) of 1100 ethenyl blocking, and Mn is the polyphenylene oxide of 2200 ethenyl blockings
(Noryl* SA9000)）.Because polyphenylene oxide is water insoluble, with the gradually volatilization of benzene solvent, in water oil phase interface polyphenylene oxide
Precipitation can be deposited or adsorbed on the surface of mesoporous silicon oxide, seal mesoporous, and after the present invention is stirred 4~6 hours, mixed liquor passes through
Water washing, suction filtration, 100~120 DEG C of vacuum drying can obtain the coating mesoporous silicon dioxide granule of polyphenylene oxide, polyphenyl in 4~6 hours
Ether is wrapped in meso-porous titanium dioxide silicon face, keeps mesoporous SiO 2 structure, effectively prevent resin enter it is mesoporous in, so as to can send out
Wave its low-dielectric energy.
In above-mentioned technical scheme, the aperture of described mesoporous silicon oxide is 2nm~9nm, and particle diameter is 20~100nm.
If specific surface area is 500~800m2/ g, two-dimensional channel, the mesopore silicon oxide that hexagonal mesoporous aperture is 7~9nm（UC-S-1）；
Specific surface area is 700m2/ g, 3 D pore canal, cubic mesoporous aperture are the mesopore silicon oxide of 6nm（UC-S-3）；Specific surface area is
1300m2/ g, two-dimensional channel, hexagonal mesoporous aperture are the mesopore silicon oxide of 2nm（UC-S-6）.
Preferably, the technique of solidification is 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220~230 DEG C/2h.It is of the invention
On the one hand preparation method successfully solves the problems, such as that existing inorganic material increases thermosets viscosity so that thermosetting resin is tieed up
Hold good manufacturability；On the other hand, under curing process of the invention, each component step-reaction in BMI performed polymers is formed excellent
Different interfacial adhesion, solves the problems, such as existing organic-inorganic two-phase poor compatibility；So as to the low dielectric span for preparing carrys out acyl
Imide resin material has good mechanical property, while keeping good hot property.
Invention additionally discloses the low dielectric bismaleimide resin system prepared according to the above method, normal temperature dielectric constant
As little as 2.6, dielectric loss as little as 0.012 shows obvious application potential in field of electronic materials.
Further, the invention also discloses a kind of preparation method of performed polymer, comprise the following steps, by bismaleimide
Amine is heated to clear solution with allyl compound, the coating mesoporous silicon dioxide granule of polyphenylene oxide is subsequently adding, in 130~150
DEG C stirring 30~50min obtain performed polymer；Being prepared as the coating mesoporous silicon dioxide granule of polyphenylene oxide, polyphenylene oxide is dissolved in
In benzene kind solvent, mesoporous silicon oxide is added, added after stirring in the aqueous solution containing surfactant, form oil-in-water body
System, stirring obtains the coating mesoporous silicon dioxide granule of polyphenylene oxide after 4~6 hours；The matter of the polyphenylene oxide and mesoporous silicon oxide
Measuring ratio is（1~3.3）∶1.
Invention additionally discloses the performed polymer prepared according to the above method and the performed polymer in dielectric materials are prepared
Application.
Compared with prior art, the invention has the advantages that：
1. the bismaleimide resin system material that prepared by the present invention not only has excellent mechanical property and hot property, more
For it is important that with substantially low dielectric properties；Compared with the individually system of addition mesoporous silicon oxide and polyphenylene oxide, use
The mesoporous silicon oxide span system material that polyphenylene oxide of the addition containing equivalent is coated has lower more stable dielectric properties, its
Obvious application potential is shown in field of electronic materials；
2. the invention in mesoporous silicon oxide adsorption polyphenylene oxide, effectively seal mesoporous, add bismaleimide
After in amine and allyl compound solution, it is to avoid resin enters mesoporous, is that the low-dielectric of product can provide safeguard, particularly,
The dielectric materials of preparation have good mechanical property, keep originally excellent hot property；
3. the preparation method of low dielectric bismaleimide resin system disclosed by the invention has that applicability is wide, operating procedure
Simple advantage；And the performed polymer for preparing can be applicable the composite material preparation process such as casting, molding, being suitable to industrialization should
With.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the mesoporous silicon oxide of embodiment 1 and the coating mesoporous silica of polyphenylene oxide；
Fig. 2 is the mesoporous silicon oxide of embodiment 1, polyphenylene oxide and the coating mesoporous silica infrared spectrum of polyphenylene oxide；
Fig. 3 is the impact fracture surface SEM figures of comparative example 1 and the material of embodiment 1；
Fig. 4 is the SEM figures of the mesoporous silicon oxide of the polyphenylene oxide of embodiment 2 cladding；
Fig. 5 is the impact fracture surface SEM figures of comparative example 2 and the material of embodiment 2.
Specific embodiment
With reference to embodiment, technical solution of the present invention will be further described.
Embodiment 1
By 2g polyphenylene oxide（Number-average molecular weight is 1100 ethenyl blocking polyphenylene oxide（PPO* MX9000-111））It is dissolved completely in
In 25ml toluene, polyphenyl ethereal solution is obtained, be subsequently adding the mesoporous silicon oxide of 0.6g（UC-S-1）, it is added to after dispersed with stirring
During mass concentration is 0.15% aqueous solution of 500ml lauryl sodium sulfate surfactants, oil-in-water system is formed.Due to
Polyphenylene oxide is water insoluble, and with the gradually volatilization of toluene solvant, the polyphenylene oxide of precipitation can be deposited or adsorbed in mesoporous silicon oxide
Surface, seal it is mesoporous.Precipitate is scrubbed after stirring 4 hours, suction filtration, and 120 DEG C of vacuum drying can obtain polyphenylene oxide in 4 hours
Filling cladding Metaporous silicon dioxide material, wherein polyphenylene oxide and mesoporous silicon oxide material quality ratio are 3.3:1.Fig. 1 is Jie
Hole silica（It is left）, the coating mesoporous silica of polyphenylene oxide（It is right）ESEM（SEM）Photo；Fig. 2 is meso-porous titanium dioxide
Silicon, polyphenylene oxide and the coating mesoporous silica of polyphenylene oxide it is infrared（FTIR）Spectrogram.
50g dimaleoyl iminos diphenyl-methane is heated with stirring to 50g diallyl bisphenols compound at 130 DEG C
Clear solution, is subsequently adding the coating mesoporous silicon dioxide granule of 1g polyphenylene oxide, about in 140 DEG C of pre-polymerization 50min under stirring condition, with
During prepolymer solution poured into flat plate mold afterwards, about 30min is vacuumized at 140 DEG C, then again according to temperature program(me) 150
DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h solidified, and curing materials are taken out from flat plate mold after natural cooling, it is
Product of the present invention.
Comparative example 1
50g dimaleoyl iminos diphenyl-methane and 50g diallyl bisphenols compound are heated with stirring in 130oC transparent
Solution, about in 140 DEG C of pre-polymerization 50min under stirring condition, during prepolymer solution then poured into flat plate mold, takes out at 140 DEG C
Vacuum about 30min, is then solidified according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h of temperature program(me) again,
After natural cooling curing materials are taken out from flat plate mold.Fig. 3 is comparative example 1（It is left）And embodiment 1（It is right）Prepared material
The SEM figures of impact fracture section, table 1 is the performance parameter of the curing materials of embodiment 1 and the curing materials of comparative example 1.
From Fig. 1（It is left）As can be seen that the surface of mesoporous silicon oxide can find micro-pore, but coated through polyphenylene oxide
Mesoporous silicon oxide（It is right）Surface due to the deposition of polyphenylene oxide, surface does not substantially observe the hole knot of mesoporous silicon oxide
Structure；Figure it is seen that the mesoporous silicon oxide of polyphenylene oxide cladding contains the characteristic absorption of polyphenylene oxide and mesoporous silicon oxide
Peak, this is proved on the mesoporous silicon oxide of polyphenylene oxide deposition；Fig. 3 is the SEM pictures of the impact fracture section of prepared material, from
It can be seen that adding the material section of the coating mesoporous silica of polyphenylene oxide coarse compared with pure resin system in right figure, illustrate that it has
Excellent mechanical property；As it can be seen from table 1 after adding the coating mesoporous silicon dioxide granule of polyphenylene oxide, the mechanical property of material
Pure resin system is superior to, particularly, adds the dielectric properties of the material of the mesoporous silicon oxide of polyphenylene oxide cladding substantially to drop
Low, this is mainly polyphenylene oxide and caused by mesoporous silicon oxide has a low dielectric properties.
The performance parameter of the material of table 1
| Performance | Comparative example 1 | Embodiment 1 |
| Impact strength (KJ/m2) | 9.9 | 10.9 |
| Fracture toughness (KIC)/MPa·m1/2 | 1.2 | 1.39 |
| Bending strength/MPa | 111 | 137 |
| 5wt% weightlessness heat decomposition temperature/DEG C（TGA methods） | 416 | 418 |
| Dielectric constant（Normal temperature, 102~106Hz） | 4.4~4.0 | 3.6~3.5 |
| Dielectric loss（Normal temperature, 102~106Hz） | 0.014~0.08 | 0.013~0.019 |
Embodiment 2
By 2g polyphenylene oxide（Number-average molecular weight is the polyphenylene oxide of 1100 ethenyl blocking（PPO* MX9000-111））It is completely dissolved
In 25ml toluene, polyphenyl ethereal solution is obtained, be subsequently adding the mesoporous silicon oxide of 1.0g（UC-S-1）, added after dispersed with stirring
To in the aqueous solution of the 500ml lauryl sodium sulfate surfactants that mass concentration is 0.2%, oil-in-water system is formed.Due to
Polyphenylene oxide is water insoluble, and with the gradually volatilization of toluene solvant, the polyphenylene oxide of precipitation can be deposited or adsorbed in mesoporous silicon oxide
Surface, seal it is mesoporous.Precipitate is scrubbed after stirring 5 hours, suction filtration, and 120 DEG C of vacuum drying can obtain polyphenylene oxide in 5 hours
Filling cladding Metaporous silicon dioxide material, wherein polyphenylene oxide and mesoporous silicon oxide material quality fraction ratio are 2:1.Fig. 4 is
The SEM photograph figure of the mesoporous silicon oxide of polyphenylene oxide cladding.
50g dimaleoyl iminos diphenyl-methane is heated with stirring to 50g diallyl bisphenols compound at 130 DEG C
Clear solution, is subsequently adding the coating mesoporous silicon dioxide granule of 4g polyphenylene oxide, about in 140 DEG C of pre-polymerization 50min under stirring condition,
During prepolymer solution then poured into flat plate mold, about 30min is vacuumized at 140 DEG C, then again according to temperature program(me)
150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h is solidified, and curing materials are taken out from flat plate mold after natural cooling.
Comparative example 2
50g dimaleoyl iminos diphenyl-methane and 50g diallyl bisphenols compound are heated with stirring at 130 DEG C transparent
Solution, adds 2.7g polyphenylene oxide and 1.3g mesoporous silicon oxides under stirring condition（It is respectively equivalent to 4g polyphenylene oxide coating mesoporous two
The content of polyphenylene oxide and mesoporous silicon oxide in silica）, about in 140 DEG C of pre-polymerization 50min, then prepolymer solution is poured into
In flat plate mold, about 30min is vacuumized at 140 DEG C, then again according to 150 DEG C/2h+180 DEG C/2h+200 of temperature program(me)
DEG C/2h+220 DEG C/2h solidified, and curing materials are taken out from flat plate mold after natural cooling.Fig. 5 is comparative example 2（It is left）And
Embodiment 2（It is right）The SEM figures of the impact fracture section of prepared material, table 2 is the performance of embodiment 2 and the material of comparative example 2
Parameter.
Figure 4, it is seen that due to the deposition of polyphenylene oxide, the pattern of the mesoporous silicon oxide of polyphenylene oxide cladding with it is mesoporous
Silica is significantly different（Fig. 1 is left）；The left and right of comparison diagram 5 in resin system it can be found that directly add meso-porous titanium dioxide
Silicon（It is left）When, resin monomer can penetrate into its hole, and add the mesoporous silicon oxide of polyphenylene oxide cladding（It is right）When, it is found that
The mesoporous silicon oxide of fracture is still present hole, and this obviously helps the low-dielectric energy for giving full play to mesoporous silicon oxide；
The as shown by data of table 2, product of the invention adds polyphenylene oxide cladding to be situated between in addition to very low-k and dielectric loss
Hole silicon dioxide granule material is compared with the excellent in mechanical performance of the material for being individually added into equivalent polyphenylene oxide and mesoporous silicon oxide, and it is former
Because being probably good dispersion of the mesoporous silicon oxide in resin system due to polyphenylene oxide coating modification, and polyphenylene oxide cladding changes
Property meso-porous titanium dioxide silicon particle and resin system interfacial contact area compared with being individually added into polyphenylene oxide and mesoporous silicon oxide
It is few therefore small to matrix cross-linked network structure destructiveness.
The performance parameter of the material of table 2
| Performance | Comparative example 2 | Embodiment 2 |
| Impact strength (KJ/m2) | 10 | 12.5 |
| Fracture toughness (KIC)/MPa·m1/2 | 1.7 | 1.9 |
| Bending strength/MPa | 165 | 177 |
| 5wt% weightlessness heat decomposition temperature/DEG C（TGA methods） | 416 | 419 |
| Dielectric constant（Normal temperature, 102~106Hz） | 3.6~3.5 | 2.9~3.2 |
| Dielectric loss（Normal temperature, 102~106Hz） | 0.012~0.016 | 0.011~0.014 |
Embodiment 3
By 2g polyphenylene oxide（Number-average molecular weight is the polyphenylene oxide (Noryl* SA9000) of 2200 ethenyl blockings）It is dissolved completely in
In 30ml toluene, polyphenyl ethereal solution is obtained, be subsequently adding the mesoporous silicon oxide of 1.4g（UC-S-3）, it is added to after dispersed with stirring
During mass concentration is 0.3% aqueous solution of 500ml Monododecylphosphate potassium surfactants, oil-in-water system is formed.By
Water insoluble in polyphenylene oxide, with the gradually volatilization of toluene solvant, the polyphenylene oxide of precipitation can be deposited or adsorbed in meso-porous titanium dioxide
The surface of silicon, fills or seals and be mesoporous.Precipitate is scrubbed after stirring 6 hours, suction filtration, and 120 DEG C of vacuum drying can be obtained for 6 hours
Metaporous silicon dioxide material is coated to polyphenylene oxide filling, wherein polyphenylene oxide is with mesoporous silicon oxide material quality fraction ratio
1.43:1。
The methyl phenyl ethers anisole of 50g dimaleoyl iminos two and 30g diallyls bisphenol S are heated with stirring at 130 DEG C transparent molten
Liquid, is subsequently adding the coating mesoporous silicon dioxide granule of 1.8g polyphenylene oxide, about in 140 DEG C of pre-polymerization 50min under stirring condition, then
During prepolymer solution poured into flat plate mold, about 30min is vacuumized at 140 DEG C, then again according to 150 DEG C of temperature program(me)/
2h+180 DEG C/2h+200 DEG C/2h+230 DEG C/2h is solidified, and curing materials are taken out from flat plate mold after natural cooling.
Comparative example 3
The methyl phenyl ethers anisole of 50g dimaleoyl iminos two and 30g diallyl bisphenol S compounds are heated with stirring in 130oC transparent
Solution, about in 140 DEG C of pre-polymerization 50min under stirring condition, during prepolymer solution then poured into flat plate mold, takes out at 140 DEG C
Vacuum about 30min, is then solidified according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+230 DEG C/2h of temperature program(me) again,
After natural cooling curing materials are taken out from flat plate mold.Table 3 is the performance parameter of embodiment 3 and the material of comparative example 3, from table 3
It can be seen that after adding the coating mesoporous silicon dioxide granule of polyphenylene oxide, the mechanical property of material is superior to pure resin system.Especially
It is that the dielectric properties of the material of the mesoporous silicon oxide of addition polyphenylene oxide cladding are substantially reduced, and this is mainly polyphenylene oxide cladding
Mesoporous silicon oxide has excellent mechanical property, hot property and low-dielectric caused.
The performance parameter of the material of table 3
| Performance | Comparative example 3 | Embodiment 3 |
| Impact strength (KJ/m2) | 13.5 | 15.7 |
| Fracture toughness (KIC)/MPa·m1/2 | 1.3 | 2.1 |
| Bending strength/MPa | 116 | 165 |
| 5wt% weightlessness heat decomposition temperature/DEG C（TGA methods） | 443 | 446 |
| Dielectric constant（Normal temperature, 102~106Hz） | 4.2~4.0 | 2.7~3.1 |
| Dielectric loss（Normal temperature, 102~106Hz） | 0.011~0.06 | 0.011~0.013 |
Embodiment 4
By 2g polyphenylene oxide（Number-average molecular weight is 17300 polyphenylene oxide (PPO* 630）It is dissolved completely in 40ml toluene, is gathered
Phenylate solution, is subsequently adding the mesoporous silicon oxide of 2g（UC-S-6）, it is 0.2% that mass concentration is added to after dispersed with stirring
In the aqueous solution of 600ml lauryl sodium sulfate surfactants, oil-in-water system is formed.Because polyphenylene oxide is water insoluble, with
The gradually volatilization of toluene solvant, the polyphenylene oxide of precipitation can be deposited or adsorbed on the surface of mesoporous silicon oxide, fill or seal
It is mesoporous.Precipitate is scrubbed after stirring 5 hours, suction filtration, and 120 DEG C of vacuum drying can obtain polyphenylene oxide filling cladding Jie for 5 hours
Hole earth silicon material, wherein polyphenylene oxide are 1 with mesoporous silicon oxide material quality fraction ratio:1.
50g dimaleoyl iminos diphenyl-methane and 25g allyl phenols epoxy resin are heated with stirring at 130 DEG C transparent
Solution, is subsequently adding the coating mesoporous silicon dioxide granule of 3g polyphenylene oxide, about in 140 DEG C of pre-polymerization 50min under stirring condition, then
During prepolymer solution poured into flat plate mold, about 30min is vacuumized at 140 DEG C, then again according to 150 DEG C of temperature program(me)/
2h+180 DEG C/2h+200 DEG C/2h+230 DEG C/2h is solidified, and curing materials are taken out from flat plate mold after natural cooling.
Comparative example 4
50g dimaleoyl iminos diphenyl-methane and 25g allyl phenols epoxy resin are heated with stirring at 130 DEG C transparent molten
Liquid, about in 140 DEG C of pre-polymerization 50min under stirring condition, during prepolymer solution then poured into flat plate mold, takes out true at 140 DEG C
Sky about 30min, is then solidified according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+230 DEG C/2h of temperature program(me) again, from
So curing materials are taken out after cooling from flat plate mold.
The performance parameter of the material of table 4
| Performance | Comparative example 4 | Embodiment 4 |
| Impact strength (KJ/m2) | 11.3 | 14.7 |
| Fracture toughness (KIC)/MPa·m1/2 | 1.15 | 1.76 |
| Bending strength/MPa | 123 | 171 |
| 5wt% weightlessness heat decomposition temperature/DEG C（TGA methods） | 452 | 460 |
| Dielectric constant（Normal temperature, 102~106Hz） | 4.3~4.7 | 2.6~3.0 |
| Dielectric loss（Normal temperature, 102~106Hz） | 0.018~0.09 | 0.012~0.013 |
Table 4 is the performance parameter of embodiment 4 and the material of comparative example 4, from table 4, it can be seen that adding polyphenylene oxide coating mesoporous two
After silicon oxide particle, the mechanical property of material is superior to pure resin system.Particularly, the meso-porous titanium dioxide of polyphenylene oxide cladding is added
The dielectric properties of the material of silicon are substantially reduced, and this mesoporous silicon oxide for being mainly polyphenylene oxide cladding has excellent mechanical property
Energy, hot property and low-dielectric can be caused.
Claims (10)
1. a kind of preparation method of low dielectric bismaleimide resin system, it is characterised in that comprise the following steps：By span
Carry out acid imide and be heated to clear solution with allyl compound, be subsequently adding the coating mesoporous silicon dioxide granule of polyphenylene oxide, stir
Obtain performed polymer；Then in performed polymer being poured into mould, 30~40min is vacuumized in 130~150 DEG C；Then temperature 150~
Solidified at 230 DEG C, obtained low dielectric bismaleimide resin system；The BMI, allyl compound,
The mass ratio of the coating mesoporous silicon dioxide granule of polyphenylene oxide is 100:（50~100）∶（2~8）.
2. the preparation method of low dielectric bismaleimide resin system according to claim 1, it is characterised in that：It is described double
Maleimide is dimaleoyl imino diphenyl-methane and/or the methyl phenyl ethers anisole of dimaleoyl imino two；The pi-allyl chemical combination
Thing is diallyl bisphenol, diallyl bisphenol S, aryl allyl alkyl phenol, polyallyl ether ketone, allyl phenol epoxy resin
Or N- pi-allyl arylamine.
3. the preparation method of low dielectric bismaleimide resin system according to claim 1, it is characterised in that：In 130
~150 DEG C of 30~50min of stirring obtain performed polymer.
4. the preparation method of low dielectric bismaleimide resin system according to claim 1, it is characterised in that polyphenylene oxide
The preparation method of coating mesoporous silicon dioxide granule is：Polyphenylene oxide is dissolved in benzene kind solvent, mesoporous silicon oxide, stirring is added
Add afterwards in the aqueous solution containing surfactant, stirring obtains the coating mesoporous silicon dioxide granule of polyphenylene oxide after 4~6 hours；
The polyphenylene oxide is with the mass ratio of mesoporous silicon oxide（1~3.3）∶1.
5. the preparation method of low dielectric bismaleimide resin system according to claim 4, it is characterised in that：Described
The molecular weight of polyphenylene oxide is 1100~20000；The mesoporous aperture of the mesopore silicon oxide be 2nm~9nm, particle diameter be 20~
100nm；The surfactant includes neopelex, lauryl sodium sulfate, Monododecylphosphate potassium.
6. the preparation method of low dielectric bismaleimide resin system according to claim 4, it is characterised in that：Polyphenylene oxide
It is 1 with the mass ratio of benzene kind solvent:（10~18）；The mass concentration of surfactant is in the aqueous solution containing surfactant
0.1~0.3%；After stirring 4~6 hours, by water washing, suction filtration, 100~120 DEG C are vacuum dried 4~6 hours mixed liquor
Obtain the coating mesoporous silicon dioxide granule of polyphenylene oxide.
7. the preparation method of low dielectric bismaleimide resin system according to claim 1, it is characterised in that：Solidification
Technique is 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220~230 DEG C/2h.
8. the low dielectric span that according to claim 1 prepared by the preparation method of low dielectric bismaleimide resin system comes
Imide resin system.
9. a kind of preparation method of performed polymer, it is characterised in that comprise the following steps：By BMI and pi-allyl chemical combination
Thing is heated to clear solution, is subsequently adding the coating mesoporous silicon dioxide granule of polyphenylene oxide, and 30~50min is stirred in 130~150 DEG C
Obtain performed polymer；The preparation method of the coating mesoporous silicon dioxide granule of polyphenylene oxide is：Polyphenylene oxide is dissolved in benzene kind solvent,
Mesoporous silicon oxide is added, is added after stirring in the aqueous solution containing surfactant, stirring obtains polyphenylene oxide after 4~6 hours
Coating mesoporous silicon dioxide granule；The polyphenylene oxide is with the mass ratio of mesoporous silicon oxide（1~3.3）∶1.
10. the performed polymer that according to claim 9 prepared by the preparation method of performed polymer.
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| CN201810977266.XA CN109232890B (en) | 2016-12-09 | 2016-12-09 | Preparation method of prepolymer for low-dielectric bismaleimide resin system |
| CN201611132719.6A CN106750297B (en) | 2016-12-09 | 2016-12-09 | A kind of low dielectric bismaleimide resin system and preparation method thereof |
| CN201810977245.8A CN109021235B (en) | 2016-12-09 | 2016-12-09 | Low-dielectric bismaleimide resin system |
| CN201810977267.4A CN109232891B (en) | 2016-12-09 | 2016-12-09 | Prepolymer for low-dielectric bismaleimide resin system |
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| CN102631884A (en) * | 2012-04-12 | 2012-08-15 | 苏州大学 | Closed mesoporous silicon oxide and preparation method of same |
| US20130115472A1 (en) * | 2011-09-22 | 2013-05-09 | Elite Material Co., Ltd. | Halogen-free resin composition, and copper clad laminate and printed circuit board using same |
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| US20100108140A1 (en) * | 2008-03-14 | 2010-05-06 | E. I. Du Pont De Nemours And Company | Device capable of thermally cooling while electrically insulating |
| CN101775139B (en) * | 2009-12-31 | 2012-02-01 | 苏州大学 | Method for preparing modified bismaleimide resin |
| CN102161829A (en) * | 2011-03-12 | 2011-08-24 | 苏州大学 | Bismaleimide resin system and preparation method thereof |
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| CN105860522A (en) * | 2016-04-20 | 2016-08-17 | 威海光威复合材料股份有限公司 | Preparation method of modified bismaleimide resin |
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| US20130115472A1 (en) * | 2011-09-22 | 2013-05-09 | Elite Material Co., Ltd. | Halogen-free resin composition, and copper clad laminate and printed circuit board using same |
| CN102631884A (en) * | 2012-04-12 | 2012-08-15 | 苏州大学 | Closed mesoporous silicon oxide and preparation method of same |
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