CN109021235A - A kind of low dielectric bismaleimide resin system - Google Patents

A kind of low dielectric bismaleimide resin system Download PDF

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CN109021235A
CN109021235A CN201810977245.8A CN201810977245A CN109021235A CN 109021235 A CN109021235 A CN 109021235A CN 201810977245 A CN201810977245 A CN 201810977245A CN 109021235 A CN109021235 A CN 109021235A
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polyphenylene oxide
low dielectric
resin system
mesoporous silicon
bismaleimide resin
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CN109021235B (en
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袁莉
顾嫒娟
梁国正
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Suzhou University
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Suzhou University
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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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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
    • 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
    • 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 systems, using bismaleimide, 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；Method disclosed by the invention has the characteristics that simple process, applicability are wide, and prepared material has a wide range of applications potentiality in Aeronautics and Astronautics and electronic field.

Description

A kind of low dielectric bismaleimide resin system
The present invention is entitled a kind of low dielectric bismaleimide resin system and preparation method thereof, the applying date is On December 9th, 2016, application No. is the divisional applications of 2016111327196 patent applications, belong to product technology part.
Technical field
The invention belongs to high-performance resin matrix technical fields, are related to a kind of low dielectric high performance resin based composites, More particularly to a kind of low dielectric bismaleimide resin system.
Background technique
Bismaleimide resin system is a kind of typical high-performance thermosetting resin, have excellent mechanical property, Hot property and electrical property etc. have application potential outstanding in Aeronautics and Astronautics field of electronic materials.With microelectric technique High speed development, the performance of existing bismaleimide resin system material are no longer satisfied high integration, the high property of more low-power consumption The development of energy electronic product, this just needs to develop more excellent performance of low dielectric high-performance bismaleimide resin system. 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 be substantially reduced.Mesoporous silicon oxide is a kind of inorganic material with pore structure, is had great Specific surface area, a large amount of Si~O~Si segment and silicone hydroxyl abundant, thus its for design have mechanical property outstanding, The material of heat resistance and dielectric properties (dielectric constant about 1.5~1.7) provides advantage.Regrettably, although mesoporous two The material of silica can be obviously improved the mechanical property even hot property of polymer matrix composites, but there is no sufficiently hairs Its low-dielectric energy advantage is waved, reason is that during material forming process, small-molecule substance can penetrate into silica In mesoporous, to be unable to fully utilize its low-dielectric energy.Further, since mesoporous silicon oxide has high specific surface area, The viscosity that can obviously increase resin system is added, resin forming craftsmanship is caused 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) is a kind of important High performance plastic resin, possesses higher glass Change transition temperature (Tg=210 DEG C), good heat resistance and dimensional stability, higher toughness, lower hydroscopicity, although PPO Addition can reduce the dielectric properties of aathermoset resin system to a certain extent, still, high level PPO addition can reduce tree Crosslink density or the other performance such as intensity of resin system and heat resistance etc., and PPO is used alone to reduce thermosetting resin body The dielectric properties effect of system is poor.
Summary of the invention
The purpose of the present invention is to provide a kind of low dielectric bismaleimide resin systems and preparation method thereof, will have Mesoporous sealing of the material of low dielectric to mesoporous silicon oxide is conducive to the low-dielectric energy for maintaining mesoporous silicon oxide, thus Promote it in the application for developing dielectric materials field.
In order to achieve the above object, the technical solution adopted by the present invention is that: a kind of low dielectric bismaleimide resin The preparation method of system, comprising the following steps: bismaleimide and allyl compound are heated to clear solution, are then added The coating mesoporous silicon dioxide granule of polyphenylene oxide, stirs to get performed polymer；Then performed polymer is poured into mold, in 130~150 DEG C Vacuumize 30~40min；Then solidified at 150~230 DEG C of temperature, obtain low dielectric bismaleimide resin System.
In the above technical solution, raw material components and quality proportioning are 100 parts of bismaleimide；Allyl compound 50 ~100 parts；2~8 parts of the coating mesoporous silica of polyphenylene oxide.
In the above technical solution, bismaleimide and allyl compound are heated with stirring at 130~140 DEG C Bright solution；It is low dielectric bismaleimide resin system that natural cooling, which obtains solidfied material, after solidification 7~9 hours.
In the above technical solution, the bismaleimide is dimaleoyl imino diphenyl-methane, span carrys out acyl Two methyl phenyl ethers anisole of imido grpup.
In the above technical solution, the allyl compound is diallyl bisphenol, diallyl bisphenol S, allyl Base aralkyl phenol, polyallyl ether ketone, allyl phenol epoxy resin, N- allyl arylamine.
In the above technical solution, performed polymer is obtained in 130~150 DEG C of 30~50min of stirring.
In the above technical solution, polyphenylene oxide the preparation method of the coating mesoporous silicon dioxide granule of polyphenylene oxide: is dissolved in benzene In class solvent, mesoporous silicon oxide is added, is added in the aqueous solution containing surfactant after stirring, forms oil-in-water system, Stirring obtained 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 the above technical solution, the mass ratio of the preferred toluene of benzene kind solvent, polyphenylene oxide and benzene kind solvent is 1: (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 are (such as: the polyphenylene oxide (PPO* that number-average molecular weight (Mn) is 17300 630) polyphenylene oxide (PPO* MX9000-111) for the ethenyl blocking that, Mn is 1100, Mn are the polyphenylene oxide of 2200 ethenyl blockings (Noryl* SA9000)).Since polyphenylene oxide is not soluble in water, with the gradually volatilization of benzene solvent, the polyphenylene oxide at water oil phase interface The surface that can deposit or be adsorbed on mesoporous silicon oxide is precipitated, sealing is mesoporous, and after the present invention stirs 4~6 hours, mixed liquor passes through The coating mesoporous silicon dioxide granule of polyphenylene oxide, polyphenyl can be obtained in 4~6 hours in water washing, suction filtration, 100~120 DEG C of vacuum drying Ether is wrapped in meso-porous titanium dioxide silicon face, keeps mesoporous SiO 2 structure, effectively prevent resin to enter in mesoporous, so as to send out Wave its low-dielectric energy.
In the above technical solution, the aperture of the mesoporous silicon oxide is 2nm~9nm, and partial size is 20~100nm. If specific surface area is 500~800m2/ g, two-dimensional channel, the mesopore silicon oxide (UC-S-1) that hexagonal mesoporous aperture is 7~9nm； Specific surface area is 700m2/ g, 3 D pore canal, the mesopore silicon oxide (UC-S-3) that cubic mesoporous aperture is 6nm；Specific surface area is 1300m2/ g, two-dimensional channel, the mesopore silicon oxide (UC-S-6) that hexagonal mesoporous aperture is 2nm.
Preferably, cured technique is 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220~230 DEG C/2h.Of the invention On the one hand preparation method successfully solves the problems, such as that existing inorganic material increases thermosetting material viscosity, so that thermosetting resin is tieed up Hold good craftsmanship；On the other hand, under curing process of the invention, each component step-reaction in BMI performed polymer is formed excellent Different interfacial adhesion solves the problems, such as existing organic-inorganic two-phase poor compatibility；To which the low dielectric span of preparation 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, room temperature dielectric constants Down to 2.6, dielectric loss shows apparent application potential down to 0.012, in field of electronic materials.
Further, the invention also discloses a kind of preparation method of performed polymer, include the following steps, by bismaleimide Amine and allyl compound are heated to clear solution, the coating mesoporous silicon dioxide granule of polyphenylene oxide are then added, 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, is added in the aqueous solution containing surfactant after stirring, forms oil-in-water body System, stirring obtained the coating mesoporous silicon dioxide granule of polyphenylene oxide after 4~6 hours；The matter of the polyphenylene oxide and mesoporous silicon oxide Amount is than being (1~3.3): 1.
Invention additionally discloses the performed polymers prepared according to the above method and the performed polymer in preparing dielectric materials Application.
Compared with prior art, the invention has the advantages that:
1. bismaleimide resin system material prepared by the present invention not only has excellent mechanical property and hot property, more For it is important that having obvious low dielectric properties；Compared with the individually system of addition mesoporous silicon oxide and polyphenylene oxide, use The mesoporous silicon oxide span system material for adding the polyphenylene oxide cladding containing equivalent has lower more stable dielectric properties, Apparent application potential is shown in field of electronic materials；
2. the invention in mesoporous silicon oxide adsorption polyphenylene oxide, effectively seal mesoporous, bismaleimide be added After in amine and allyl compound solution, avoids resin from entering mesoporous, can be provided safeguard for the low-dielectric of product, 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 wide, operating procedure with applicability Simple advantage；And the performed polymer of preparation can be applicable in the composite material preparation process such as casting, molding, answer suitable for industrialization With.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of 1 mesoporous silicon oxide of embodiment and the coating mesoporous silica of polyphenylene oxide；
Fig. 2 is 1 mesoporous silicon oxide of embodiment, polyphenylene oxide and the coating mesoporous silica infrared spectrum of polyphenylene oxide；
Fig. 3 is that the impact fracture surface SEM of 1 material of comparative example 1 and embodiment schemes；
Fig. 4 is the SEM figure of the mesoporous silicon oxide of 2 polyphenylene oxide of embodiment cladding；
Fig. 5 is that the impact fracture surface SEM of 2 material of comparative example 2 and embodiment schemes.
Specific embodiment
Below with reference to embodiment, technical solution of the present invention will be further described.
Embodiment 1
2g polyphenylene oxide (the ethenyl blocking polyphenylene oxide (PPO* MX9000-111) that number-average molecular weight is 1100) is dissolved completely in In 25ml toluene, polyphenyl ethereal solution is obtained, the mesoporous silicon oxide (UC-S-1) of 0.6g is then added, is added to after being dispersed with stirring In the aqueous solution for the 500ml lauryl sodium sulfate surfactant that mass concentration is 0.15%, oil-in-water system is formed.Due to Polyphenylene oxide is not soluble in water, and with the gradually volatilization of toluene solvant, the polyphenylene oxide of precipitation can deposit or be adsorbed on mesoporous silicon oxide Surface, seal it is mesoporous.Precipitate is washed after stirring 4 hours, filters, and polyphenylene oxide can be obtained in 4 hours in 120 DEG C of vacuum drying Filling cladding Metaporous silicon dioxide material, wherein polyphenylene oxide and mesoporous silicon oxide material quality ratio are 3.3:1.Fig. 1 is to be situated between Scanning electron microscope (SEM) photo of hole silica (left side), the coating mesoporous silica of polyphenylene oxide (right side)；Fig. 2 is meso-porous titanium dioxide Infrared (FTIR) spectrogram of silicon, polyphenylene oxide and the coating mesoporous silica of polyphenylene oxide.
50g dimaleoyl imino diphenyl-methane is heated with stirring to 50g diallyl bisphenol compound at 130 DEG C Then the coating mesoporous silicon dioxide granule of 1g polyphenylene oxide is added in clear solution, about in 140 DEG C of pre-polymerization 50min under stirring condition, with Prepolymer solution is 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, curing materials are taken out from flat plate mold after natural cooling, are Product of the present invention.
Comparative example 1
50g dimaleoyl imino diphenyl-methane is heated with stirring in 130oC with 50g diallyl bisphenol compound transparent Prepolymer solution is then poured into flat plate mold, is taken out at 140 DEG C about in 140 DEG C of pre-polymerization 50min under stirring condition by solution Then vacuum about 30min is solidified according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220 DEG C/2h of temperature program(me) again, Curing materials are taken out from flat plate mold after natural cooling.Fig. 3 is comparative example 1(left) and the right side embodiment 1() material prepared The SEM of impact fracture section schemes, and table 1 is the performance parameter of 1 curing materials of 1 curing materials of embodiment and comparative example.
From Fig. 1 (left side) as can be seen that the surface of mesoporous silicon oxide can find micro-pore, but through polyphenylene oxide cladding Due to the deposition of polyphenylene oxide, surface does not obviously observe the hole knot of mesoporous silicon oxide on the surface of mesoporous silicon oxide (right side) 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 picture of the impact fracture section of material prepared, from It can be seen that the material section that the coating mesoporous silica of polyphenylene oxide is added is 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 the coating mesoporous silicon dioxide granule of polyphenylene oxide is added, the mechanical property of material It is superior to pure resin system, in particular, the dielectric properties that the material of the mesoporous silicon oxide of polyphenylene oxide cladding is added obviously drop Low, this is mainly that polyphenylene oxide and mesoporous silicon oxide have caused by low dielectric properties.
The performance parameter of 1 material of table
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 thermal decomposition temperature/DEG C (TGA method) 416 418
Dielectric constant (room temperature, 102~106Hz) 4.4~4.0 3.6~3.5
Dielectric loss (room temperature, 102~106Hz) 0.014~0.08 0.013~0.019
Embodiment 2
2g polyphenylene oxide (polyphenylene oxide (PPO* MX9000-111) for the ethenyl blocking that number-average molecular weight is 1100) is completely dissolved In 25ml toluene, polyphenyl ethereal solution is obtained, the mesoporous silicon oxide (UC-S-1) of 1.0g is then added, is added after being dispersed with stirring In aqueous solution to mass concentration for 0.2% 500ml lauryl sodium sulfate surfactant, oil-in-water system is formed.Due to Polyphenylene oxide is not soluble in water, and with the gradually volatilization of toluene solvant, the polyphenylene oxide of precipitation can deposit or be adsorbed on mesoporous silicon oxide Surface, seal it is mesoporous.Precipitate is washed after stirring 5 hours, filters, and polyphenylene oxide can be obtained in 5 hours in 120 DEG C of vacuum drying Filling cladding Metaporous silicon dioxide material, wherein polyphenylene oxide and mesoporous silicon oxide material quality score ratio are 2:1.Fig. 4 is The SEM photograph figure of the mesoporous silicon oxide of polyphenylene oxide cladding.
50g dimaleoyl imino diphenyl-methane is heated with stirring to 50g diallyl bisphenol compound at 130 DEG C Then the coating mesoporous silicon dioxide granule of 4g polyphenylene oxide is added in clear solution, about in 140 DEG C of pre-polymerization 50min under stirring condition, Then prepolymer solution is 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 takes out curing materials from flat plate mold after natural cooling.
Comparative example 2
50g dimaleoyl imino diphenyl-methane is heated with stirring at 130 DEG C with 50g diallyl bisphenol compound transparent Solution is added 2.7g polyphenylene oxide under stirring condition and 1.3g mesoporous silicon oxide (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, curing materials are taken out from flat plate mold after natural cooling.Fig. 5 is comparative example 2(left) and Embodiment 2(is right) the SEM figure of the impact fracture section of material prepared, table 2 is the performance of 2 material of embodiment 2 and comparative example 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)；5 left and right of comparison diagram in resin system it can be found that be directly added meso-porous titanium dioxide When silicon (left side), resin monomer can penetrate into its hole, and be added polyphenylene oxide cladding mesoporous silicon oxide (right side) when, it is found that The mesoporous silicon oxide of fracture still has hole, this obviously helps the low-dielectric energy for giving full play to mesoporous silicon oxide； Table 2 statistics indicate that, product of the invention is added polyphenylene oxide cladding and is situated between in addition to having very other than low-k and dielectric loss Excellent in mechanical performance of the hole silicon dioxide granule material compared with the material for being individually added into equivalent polyphenylene oxide and mesoporous silicon oxide, original Because may be good dispersion of the mesoporous silicon oxide in resin system due to polyphenylene oxide coating modification, and polyphenylene oxide cladding changes The interfacial contact area of the meso-porous titanium dioxide silicon particle of property and resin system is compared with being individually added into polyphenylene oxide and mesoporous silicon oxide It is few therefore small to matrix cross-linked network structure extent of the destruction.
The performance parameter of 2 material of table
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 thermal decomposition temperature/DEG C (TGA method) 416 419
Dielectric constant (room temperature, 102~106Hz) 3.6~3.5 2.9~3.2
Dielectric loss (room temperature, 102~106Hz) 0.012~0.016 0.011~0.014
Embodiment 3
2g polyphenylene oxide (polyphenylene oxide (Noryl* SA9000) that number-average molecular weight is 2200 ethenyl blockings) is dissolved completely in In 30ml toluene, polyphenyl ethereal solution is obtained, the mesoporous silicon oxide (UC-S-3) of 1.4g is then added, is added to after being dispersed with stirring In the aqueous solution for the 500ml Monododecylphosphate potassium surfactant that mass concentration is 0.3%, oil-in-water system is formed.By Not soluble in water in polyphenylene oxide, with the gradually volatilization of toluene solvant, the polyphenylene oxide of precipitation can deposit or be adsorbed on meso-porous titanium dioxide The surface of silicon is filled or is sealed and is mesoporous.Precipitate is washed after stirring 6 hours, filters, and 120 DEG C of vacuum drying can obtain for 6 hours Cladding Metaporous silicon dioxide material is filled to polyphenylene oxide, wherein polyphenylene oxide is with mesoporous silicon oxide material quality score ratio 1.43:1。
Two methyl phenyl ethers anisole of 50g dimaleoyl imino is heated with stirring at 130 DEG C with 30g diallyl bisphenol S transparent molten Then the coating mesoporous silicon dioxide granule of 1.8g polyphenylene oxide is added in liquid, about in 140 DEG C of pre-polymerization 50min under stirring condition, then Prepolymer solution is 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 takes out curing materials from flat plate mold after natural cooling.
Comparative example 3
Two methyl phenyl ethers anisole of 50g dimaleoyl imino is heated with stirring in 130oC with 30g diallyl bisphenol S compound transparent Prepolymer solution is then poured into flat plate mold, is taken out at 140 DEG C about in 140 DEG C of pre-polymerization 50min under stirring condition by solution Then vacuum about 30min is solidified according to 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+230 DEG C/2h of temperature program(me) again, Curing materials are taken out from flat plate mold after natural cooling.Table 3 is the performance parameter of 3 material of embodiment 3 and comparative example, from table 3 It can be seen that the mechanical property of material is superior to pure resin system after the coating mesoporous silicon dioxide granule of polyphenylene oxide is added.Especially It is that the dielectric properties that the material for the mesoporous silicon oxide that polyphenylene oxide coats is added are substantially reduced, this is mainly what polyphenylene oxide coated Mesoporous silicon oxide has caused by excellent mechanical property, hot property and low-dielectric energy.
The performance parameter of 3 material of table
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 thermal decomposition temperature/DEG C (TGA method) 443 446
Dielectric constant (room temperature, 102~106Hz) 4.2~4.0 2.7~3.1
Dielectric loss (room temperature, 102~106Hz) 0.011~0.06 0.011~0.013
Embodiment 4
By 2g polyphenylene oxide, (polyphenylene oxide (PPO* 630) that number-average molecular weight is 17300 is dissolved completely in 40ml toluene, is gathered Then the mesoporous silicon oxide (UC-S-6) of 2g is added in phenylate solution, it is 0.2% that mass concentration is added to after being dispersed with stirring In the aqueous solution of 600ml lauryl sodium sulfate surfactant, oil-in-water system is formed.Since polyphenylene oxide is not soluble in water, with The gradually volatilization of toluene solvant, the polyphenylene oxide of precipitation can deposit or be adsorbed on the surface of mesoporous silicon oxide, filling or sealing It is mesoporous.Precipitate is washed after stirring 5 hours, filters, and 120 DEG C of vacuum drying can be obtained polyphenylene oxide filling cladding for 5 hours and be situated between Hole earth silicon material, wherein polyphenylene oxide and mesoporous silicon oxide material quality score ratio are 1:1.
50g dimaleoyl imino diphenyl-methane is heated with stirring at 130 DEG C with 25g allyl phenol epoxy resin transparent Then the coating mesoporous silicon dioxide granule of 3g polyphenylene oxide is added in solution, about in 140 DEG C of pre-polymerization 50min under stirring condition, then Prepolymer solution is 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 takes out curing materials from flat plate mold after natural cooling.
Comparative example 4
50g dimaleoyl imino diphenyl-methane is heated with stirring at 130 DEG C with 25g allyl phenol epoxy resin transparent molten Liquid then pours into prepolymer solution in flat plate mold about in 140 DEG C of pre-polymerization 50min under stirring condition, takes out at 140 DEG C true 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 from flat plate mold after cooling.
The performance parameter of 4 material of table
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 thermal decomposition temperature/DEG C (TGA method) 452 460
Dielectric constant (room temperature, 102~106Hz) 4.3~4.7 2.6~3.0
Dielectric loss (room temperature, 102~106Hz) 0.018~0.09 0.012~0.013
Table 4 is the performance parameter of 4 material of embodiment 4 and comparative example, from table 4, it can be seen that polyphenylene oxide coating mesoporous two is added After silicon oxide particle, the mechanical property of material is superior to pure resin system.In particular, the meso-porous titanium dioxide of polyphenylene oxide cladding is added The dielectric properties of the material of silicon are substantially reduced, this is mainly the mesoporous silicon oxide of polyphenylene oxide cladding with excellent mechanical property Caused by energy, hot property and low-dielectric energy.

Claims (7)

1. a kind of low dielectric bismaleimide resin system, which is characterized in that the low dielectric bismaleimide resin Then the preparation method of system is added the following steps are included: bismaleimide and allyl compound are heated to clear solution The coating mesoporous silicon dioxide granule of polyphenylene oxide, stirs to get performed polymer；Then performed polymer is poured into mold, in 130~150 DEG C Vacuumize 30~40min；Then solidified at 150~230 DEG C of temperature, obtain low dielectric bismaleimide resin System；The mass ratio of the coating mesoporous silicon dioxide granule of the bismaleimide, allyl compound, polyphenylene oxide is 100: (50 ~100): (2~8).
2. low dielectric bismaleimide resin system according to claim 1, it is characterised in that: the bismaleimide For two methyl phenyl ethers anisole of dimaleoyl imino diphenyl-methane and/or dimaleoyl imino；The allyl compound is two allyls Base bisphenol-A, diallyl bisphenol S, aryl allyl alkyl phenol, polyallyl ether ketone, allyl phenol epoxy resin or N- allyl Base arylamine.
3. low dielectric bismaleimide resin system according to claim 1, it is characterised in that: stirred in 130~150 DEG C 30~50min obtains performed polymer.
4. low dielectric bismaleimide resin system according to claim 1, which is characterized in that polyphenylene oxide coating mesoporous two Silicon oxide particle the preparation method comprises the following steps: polyphenylene oxide is dissolved in benzene kind solvent, mesoporous silicon oxide is added, is added and contains after stirring In the aqueous solution of surfactant, stirring obtained the coating mesoporous silicon dioxide granule of polyphenylene oxide after 4~6 hours；The polyphenylene oxide Mass ratio with mesoporous silicon oxide is (1~3.3): 1.
5. low dielectric bismaleimide resin system according to claim 4, it is characterised in that: point of the polyphenylene oxide Son amount is 1100~20000；The mesoporous aperture of the mesopore silicon oxide is 2nm~9nm, and partial size is 20~100nm；The surface Activating agent includes neopelex, lauryl sodium sulfate, Monododecylphosphate potassium.
6. low dielectric bismaleimide resin system according to claim 4, it is characterised in that: polyphenylene oxide and benzene kind solvent Mass ratio be 1: (10~18)；The mass concentration of surfactant is 0.1~0.3% in aqueous solution containing surfactant； After stirring 4~6 hours, by water washing, suction filtration, 100~120 DEG C of vacuum drying polyphenylene oxide is can be obtained in 4~6 hours in mixed liquor Coating mesoporous silicon dioxide granule.
7. low dielectric bismaleimide resin system according to claim 1, it is characterised in that: cured technique is 150 DEG C/2h+180 DEG C/2h+200 DEG C/2h+220~230 DEG C/2h.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110713616A (en) * 2019-09-24 2020-01-21 苏州益可泰电子材料有限公司 Material for electronics and use thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110760292B (en) * 2019-09-24 2021-02-09 江苏立一新材料科技有限公司 Heat-resistant friction material and application thereof
CN110643321B (en) * 2019-09-24 2022-03-29 苏州益可泰电子材料有限公司 Electronic material glue solution and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102161829A (en) * 2011-03-12 2011-08-24 苏州大学 Bismaleimide resin system and preparation method thereof
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
CN103965606A (en) * 2013-02-04 2014-08-06 联茂电子股份有限公司 Low dielectric material
US20140275377A1 (en) * 2013-03-18 2014-09-18 Iteq Corporation Dielectric material with low dielectric loss
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

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050049350A1 (en) * 2003-08-25 2005-03-03 Sandeep Tonapi Thin bond-line silicone adhesive composition and method for preparing the same
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
CN102627857B (en) * 2012-04-20 2014-05-14 苏州大学 Modified thermosetting resin and preparation method thereof
CN105968808B (en) * 2016-07-05 2018-08-24 苏州大学 A kind of self-repair resin based composites and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102161829A (en) * 2011-03-12 2011-08-24 苏州大学 Bismaleimide resin system and preparation method thereof
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
CN103965606A (en) * 2013-02-04 2014-08-06 联茂电子股份有限公司 Low dielectric material
US20140275377A1 (en) * 2013-03-18 2014-09-18 Iteq Corporation Dielectric material with low dielectric loss
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110713616A (en) * 2019-09-24 2020-01-21 苏州益可泰电子材料有限公司 Material for electronics and use thereof
CN110713616B (en) * 2019-09-24 2022-03-29 苏州益可泰电子材料有限公司 Material for electronics and use thereof

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