CN108003564A - High frequency low-dielectric functionalization graphene/main chain benzoxazine compound resin and its in-situ inserted solution preparation method - Google Patents
High frequency low-dielectric functionalization graphene/main chain benzoxazine compound resin and its in-situ inserted solution preparation method Download PDFInfo
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- CN108003564A CN108003564A CN201711094582.4A CN201711094582A CN108003564A CN 108003564 A CN108003564 A CN 108003564A CN 201711094582 A CN201711094582 A CN 201711094582A CN 108003564 A CN108003564 A CN 108003564A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/34—Condensation polymers of aldehydes or ketones with monomers covered by at least two of the groups C08L61/04, C08L61/18 and C08L61/20
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
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- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The present invention relates to high frequency low-dielectric functionalization graphene/main chain benzoxazine compound resin and its in-situ inserted solution preparation method.Preparation method：Functional graphene oxide is scattered in organic solvent by ultra-sonic dispersion method, obtains the functional graphene oxide uniform dispersion of 0.1~10g/L；Main chain benzoxazine binary or ternary resin prepolymer are dissolved in corresponding organic solvent, obtain the prepolymer solution that mass concentration is 10~30%；Functional graphene oxide dispersion liquid and prepolymer solution are carried out blending to be uniformly mixed liquid so that graphene oxide or functional graphene oxide and main chain benzoxazine binary or ternary resin performed polymer quality ratio are 0.1~1 in mixed liquor：99~99.9；Gained mixed liquor is reacted into 2~8h at 80~140 DEG C, then at 100~220 DEG C of 4~24h of curing reaction.Compound resin hardening time of the invention is short, cures ungauged regions, and nano-particle good dispersion, has low-k, low-dielectric loss, good heat resistance, moisture-proof and mechanical performance.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of functional graphene oxide strengthens main chain benzo
Oxazine compound resin and its in-situ inserted solution preparation method.
Background technology
Benzoxazine is a kind of macromolecule containing heterocycle structure using phenols, aldehydes and primary amine compound as Material synthesis
Monomer, the ring-opening polymerisation under heating and/or catalyst action, the net structure of the nitrogenous and similar phenolic resin of generation are referred to as poly-
Benzoxazine or benzoxazine colophony.Benzoxazine colophony not only has good flame retardant effect and chemical-resistance, but also has
There are low-shrinkage, low-k and flexible MOLECULE DESIGN, and can be heating and curing in the case of no catalyst,
And released without small molecule.But benzoxazine colophony is in practical applications there is also some shortcomings, as crosslink density is low；Curing reaction
Temperature is high, hardening time length；Common benzoxazine resin after polymerization is more crisp；Hot property also needs to be further improved.
In the recent period, a kind of backbone chain type benzoxazine colophony of new structure is got the attention, i.e. the master of its synthon
Han You oxazine rings or its open-loop products in chain, homopolymer and its copolymer chain.Backbone chain type benzoxazine (main chain
Benzoxazine a kind of new benzoxazine colophony to have grown up since being) bimillennium, chemically structure design and should
There is basic difference with aspect of performance and traditional single functionality and bifunctionality benzoxazine colophony.Traditional single functionality and
Have on bifunctionality benzoxazine monomer and only 1 or 2 Ge oxazine rings, main chain benzoxazine monomer contain 2n oxazine ring.
Therefore, main chain benzoxazine monomer is intended to be crosslinked and obtain high molecular weight and outstanding toughness, and this Ben Bing Evil
Piperazine monomer can be dissolved in solvent, can also be processed in the molten state, and the material after being heating and curing is still thermosetting polymer.Cause
Have some advantages of thermosetting resin and thermoplastic resin concurrently for backbone chain type benzoxazine colophony, have a good application prospect,
It can be used as Electronic Packaging, printed circuit board (PCB), aviation and membrane material.In order to meet the prior art to low-k, low
The material of requirements at the higher level needs in terms of the comprehensive performances such as dielectric loss, high-fire resistance, high flame resistance and pliability, construct binary,
Terpolymer resin resin system, study on the modification tool for composite are of great significance.
The content of the invention
The technical problems to be solved by the invention are to be directed to above-mentioned deficiency existing in the prior art, there is provided a kind of high frequency is low
Dielectricity functional graphene oxide strengthens main chain benzoxazine compound resin and its in-situ inserted solution preparation method.
In order to solve the above technical problems, technical solution provided by the invention is：
A kind of functional graphene oxide enhancing main chain benzoxazine compound resin is provided, it is functional graphene oxide
Modified main chain benzoxazine/hydrocarbon resin binary resin, or functional graphene oxide are modified main chain benzoxazine/asphalt mixtures modified by epoxy resin
Fat/hydrocarbon resin ternary resin, by weight 0.1~5 part of functional graphene oxide, main chain benzoxazine/hydrocarbon resin
Binary resin or main chain benzoxazine/epoxy resin/5~99.9 parts of hydrocarbon resin ternary resin；The functionalization oxidation stone
Black alkene is carboxylated graphene oxide or amination graphene oxide；
The main chain benzoxazine/hydrocarbon resin binary resin is by 50~90 parts by weight of main chain benzoxazine and hydrocarbon tree
The main chain benzoxazine that 10~50 parts by weight cross-linked polymeric of fat obtains/hydrocarbon resin binary performed polymer cures；Described
Main chain benzoxazine/epoxy resin/hydrocarbon resin ternary resin is by 50~80 parts by weight of main chain benzoxazine；Epoxy resin 10~
20 parts by weight；Main chain benzoxazine/epoxy resin/hydrocarbon resin ternary that 10~30 parts by weight cross-linked polymeric of hydrocarbon resin obtains
What copolymerization system cured.
By such scheme, main chain benzoxazine of the present invention has with lower structure：
For DDM type main chain benzoxazines,
OrFor ODA type main chain benzoxazines.
Wherein n=2.5~20.
By such scheme, epoxy resin of the present invention is following one of which or its combination：It is bisphenol A epoxide resin, double
Phenol F epoxy resin, bisphenol-s epoxy resin, novolac epoxy resin, bisphenol-A phenolic epoxy resin, bisphenol F phenolic epoxy resin,
O-cresol epoxy resin, trifunctional epoxy resin, four-functional group epoxy resin, polyfunctional epoxy resin, dicyclopentadiene
Epoxy resin, paraxylene epoxy resin, naphthalene type epoxy resin, biphenyl novolac epoxy resin, isocyanate modified epoxy resin
And phenol benzaldehyde epoxy resin.
By such scheme, hydrocarbon resin of the present invention is following one of which or its combination：Polybutadiene, butylbenzene
Resin, phenylethylene-maleic anhydride, styrene-butadiene copolymer, cyclic olefin copolymer, styrene-isoprene copolymerization
Thing, polyisoprene rubber, styrene-butadiene-divinyl benzene copolymer, hydrogenated diene-butadiene-styrene copolymer
Thing.
By such scheme, the preparation method of above-mentioned main chain benzoxazine compound resin is：Main chain is added in reaction vessel
50~80 parts by weight of benzoxazine；10~20 parts by weight of epoxy resin；10~30 parts by weight of hydrocarbon resin, and be scattered in and have
In solvent, 1~6h is reacted at 80~110 DEG C, obtains the compound tree of main chain benzoxazine that solid content is 30wt%~70wt%
Fat performed polymer, is put into baking oven by gained resin prepolymer and carries out temperature programming curing, main chain benzoxazine main chain is obtained after curing
Benzoxazine/epoxy resin/hydrocarbon resin tri compound resin；
50~90 parts by weight of main chain benzoxazine are added in reaction vessel；10~50 parts by weight of hydrocarbon resin；And by its
It is scattered in organic solvent, reacts 1~6h at 80~110 DEG C, obtains the main chain Ben Bing Evil that solid content is 30wt%~70wt%
Piperazine compound resin performed polymer, is put into baking oven by gained resin prepolymer and carries out temperature programming curing, main chain benzo is obtained after curing
Oxazine main chain benzoxazine/hydrocarbon resin binary compound resin.
By such scheme, organic solvent of the present invention is acetone, toluene, dimethylbenzene, ethanol, chloroform, dimethyl
The mixture of any one or more in formamide, Isosorbide-5-Nitrae-dioxane.
By such scheme, the carboxylated graphene oxide be by graphite oxide ultrasonic disperse in alcohol solvent, obtain
The graphene oxide solution being effectively peeled off, carries out chemical modification to graphene oxide solution by chloroactic acid method and obtains；It is described super
Sound is separated into 10~30min of ultrasound under the conditions of ice-water bath, and ultrasonic power is 400~800W；
The amination graphene oxide is adds graphene oxide into solvent dimethylformamide, through ultrasonic disperse
Obtain the graphene oxide dispersion of 1~4mg/mL, then add diamine monomer into the dispersion liquid, wherein diamine monomer with
The mass ratio of graphite oxide is 1.5~3：1, the mass ratio of coupling agent, coupling agent and graphite oxide is added after being sufficiently mixed uniformly
For 5~8:100, and in 50~70 DEG C of 6~10h of back flow reaction, products therefrom is washed with ethanol, filtered, is dry after reaction
Obtain；
By such scheme, the graphene oxide is using natural flake graphite as raw material, passes through improved Hummers side
Legal system obtains graphite oxide.The natural flake graphite particle diameter is 30~40 μm.
By such scheme, the in-situ inserted solution of above-mentioned functional graphene oxide enhancing main chain benzoxazine compound resin
Preparation method, step are：Functional graphene oxide is scattered in organic solvent by ultra-sonic dispersion method, obtain 0.1~
The functional graphene oxide uniform dispersion of 10g/L；Main chain benzoxazine binary or ternary resin prepolymer are dissolved in accordingly
In organic solvent, the prepolymer solution that mass concentration is 10~30% is obtained；
Functional graphene oxide dispersion liquid and prepolymer solution are carried out blending to be uniformly mixed liquid so that mixed liquor
Middle graphene oxide or functional graphene oxide and main chain benzoxazine binary or ternary resin performed polymer quality ratio for 0.1~
1：99~99.9；
Gained mixed liquor is reacted into 2~8h at 80~140 DEG C, then at 100~220 DEG C of 4~24h of curing reaction, is obtained
Functional graphene oxide strengthens main chain benzoxazine compound resin.
In the present invention：Main chain benzoxazine monomer contains 2n oxazine ring, the reaction for the cross-linking reaction that its open loop produces
Site is significantly increased, and more chemistry can occur with the carboxyl functional group that contains in other resins in binary or ternary system etc.
Bonding action, is hereby based on the unique texture of main chain benzoxazine and increasing for copolyreaction, makes binary or tri compound resin
The chemical crosslinking effect enhancing of system, greatly improves the crosslink density of compound resin, and can be into based on their synergistic effect
One step improves hot property and dielectric properties.
Specifically, binary system is built using main chain benzoxazine monomer and hydrocarbon resin, or uses main chain benzoxazine
Monomer, epoxy resin and hydrocarbon resin structure ternary system, by regulating and controlling to match dosage, on the one hand, main chain benzoxazine monomer,
Epoxy resin and hydrocarbon resin carry out cross-linking reaction, obtain based on main chain benzoxazine, and with interpenetrating networks (IPN) knot
The compound resin system of structure, still further aspect, proportioning of the invention regulation and control can make backbone chain type benzoxazine colophony in polymerization process
The polarity phenolic hydroxyl group that polymerization produces is consumed, and thus makes the compound resin of acquisition have high-fire resistance, high flame resistance and flexible
Property.
The invention introduces hydrocarbon resin in backbone chain type benzoxazine colophony, and hydrocarbon resin can be in main chain benzo
Autohemagglutination is completed in oxazine resin polymerization solidification process, interpenetrating networks (IPN) structure is formed with benzoxazine colophony, so as to effectively carry
The crosslink density and resistance to elevated temperatures of high compound resin.Hydrocarbon resin compound with regular structure and the Long carbon chain chemistry knot containing low polarity
Structure, its introducing can be improved the dielectric properties of whole compound resin system.In addition, the carbonyl function that hydrocarbon resin contains
Group can carry out reaction generation aromatic ester with the phenolic hydroxyl group of benzoxazine, form chemical crosslinking structure, further improve copolymerization tree
The crosslink density of fat, this also causes the thermal property of compound resin and mechanical performance to have great lifting.Meanwhile backbone chain type benzene
The reduction of Bing oxazine resin polarity phenolic hydroxyl groups functional group is also beneficial to the raising of compound resin dielectric properties.Epoxy resin has soft
The features such as good toughness, high crosslink density, epoxy resin carries out copolymerization with main chain benzoxazine colophony can improve main chain benzene and Evil
The toughness and crosslink density of piperazine resin.This is because the phenolic hydroxyl group that the open loop of main chain benzoxazine colophony produces can be with epoxy resin
Reaction, under the catalytic action of tertiary amine, the homopolymerization of epoxy resin can be suppressed, so that epoxy-functional participates in master
In chain benzoxazine colophony network structure, the crosslink density of main chain benzoxazine colophony is added.Moreover, polymerization process consumes
The polarity phenolic hydroxyl group that the polymerization of backbone chain type benzoxazine colophony produces, advantageously reduces the dielectric constant and dielectric damage of copolymer resins
Consumption.
To sum up, every kind of resin in backbone chain type benzoxazine/epoxy resin/hydrocarbon resin ternary resin all respectively has its property
Can, and interact, influence each other.Except above-mentioned backbone chain type benzoxazine colophony respectively with epoxy resin, hydrocarbon resin
Reaction is outer, and epoxy resin, equivalent to diluent, can reduce the viscosity of system, improve ternary resin system in ternary resin
Processing performance.And hydrocarbon resin is both the curing agent of epoxy resin, and the catalyst of main chain benzoxazine colophony, can be effective
Reduction system solidification temperature, improves the crosslink density of compound resin, so as to further improve heat while improving processing performance
Performance and dielectric properties.Therefore, the combination of each group composition and ratio regulate and control in ternary resin system provided by the invention, to compound
The structure of resin has a very big impact with performance.
Further, functional graphene oxide (carboxylated graphene oxide, amination graphene oxide) surface all contains
There are substantial amounts of oxy radical or amino group, not only can participate in main chain benzene in main chain benzoxazine monomer ring opening polymerisation process
In the network structure of Bing oxazine resins, actively impact is produced to the chain growth of resin, so that the curing degree of matrix resin is improved,
Intermolecular hydrogen bonding effect, reinforced resin can be also produced with the hydroxyl and tertiary amine groups produced after main chain benzoxazine colophony ring-opening polymerisation
The intramolecular and intermolecular force of network structure, so as to improve the glass transition temperature of composite material, heat decomposition temperature, residual
The hot propertys such as carbon rate, while the introducing of functional graphene oxide can consume the polarity that the polymerization of backbone chain type benzoxazine colophony produces
Phenolic hydroxyl group, advantageously reduces the dielectric constant and dielectric loss of copolymer resins.And the nanometer sheet such as appropriate functional graphene oxide
The introducing of layer, can form pore space structure in compound resin system, and reaching can utilize the low-k raising of air whole
The dielectric properties of a compound resin system, so that nanocomposite has under the conditions of high-frequency electromagnetic wave (10GHZ)
Lower dielectric constant (1.2~2.4) and dielectric loss (0.001~0.005).
The beneficial effects of the present invention are：
1st, the functional graphene oxide enhancing main chain benzoxazine compound resin prepared by the present invention significantly reduces solid
Change temperature, accelerate solidification rate, cure ungauged regions, and improve glass transition temperature, there is low-k, low Jie
Electrical loss, good heat resistance, moisture-proof, mechanical performance and electric property.Particularly in view of main chain benzoxazine, compound resin
The contribution of synergistic effect and functionalization graphene to dielectric properties, nanocomposite have under the conditions of high-frequency electromagnetic wave
Lower dielectric constant (1.2~2.4) and dielectric loss (0.001~0.005), so that the nanocomposite is in microwave
The emerging fields such as communication have application prospect.Functional graphene oxide strengthens the solidification temperature of main chain benzoxazine compound resin
For 210~240 DEG C, glass transition temperature is 285~350 DEG C, and tensile strength is 145~190MPa, the dielectric under 10GHz
Constant is between 1.2~2.4, and dielectric loss is between 0.001~0.005；
2nd, the present invention is compound using in-situ solution preparation method preparation functional graphene oxide enhancing main chain benzoxazine
Resin, graphene oxide are easily dispersed, and strengthen main chain benzo suitable for the high functional graphene oxide of graphene oxide volume
The preparation of oxazine composite resin material, in addition, functional graphene oxide after solvent supersonic, be easily peeled off into monolithic layer or
Interlamellar spacing increases.Moreover, it is easily dispersed in resin matrix, it is easier to which generation chemically and physically interacts, under solvent state
The resin of preparation is compatible good.Preparation method technique is simple, raw material is easy to get.
Brief description of the drawings
Functional graphene oxide enhancing main chain benzoxazine/epoxy that Fig. 1 is prepared for the embodiment of the present invention/hydrocarbon compound
The DSC curve of resin.Wherein, a is the main chain benzoxazine/epoxy/hydrocarbon compound resin for being not added with carboxylated graphene oxide
Curing DSC curve, and a ', b ' the carboxylated graphene oxide enhancing main chain benzo that to be respectively embodiment 4 and embodiment 5 prepare
The curing DSC curve of oxazine/epoxy/hydrocarbon compound resin.As shown in the figure, after adding carboxylated graphene, tri compound tree
The cure peak temperature of fat reduces 20 DEG C or so, shows that carboxylated graphene oxide can effectively facilitate main chain benzoxazine three
The curing of first resin, so as to reduce solidification temperature, improves curing degree.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made with reference to embodiment
It is described in further detail.
The preparation of graphene oxide：
Using the natural flake graphite of 48 μm of particle diameter as raw material, graphite oxide is made by improved Hummers methods, be by
Natural flake graphite is added in the concentrated sulfuric acid, and stirring, add sodium nitrate and potassium permanganate；Specially press quality % ratios, natural scale
Graphite accounts for 2, and sodium nitrate accounts for 1, and potassium permanganate accounts for 7, and the concentrated sulfuric acid that concentration is 98% accounts for 90；Control 4 DEG C of concentrated sulfuric acid temperature, reaction
60min；32 DEG C are warming up to, reacts 30min；Then at 100 DEG C of reaction 30min；Reaction product passes through centrifuge washing to sulfate radical-free
After ion, in 40 DEG C of drying, graphite oxide is made.Graphite oxide is scattered in alcohol solvent, solution surpasses through overpower 500W
Sonication 1h, the graphene oxide solution being effectively peeled off.
The preparation of carboxylated graphene oxide：
Graphite oxide is made according to the method described above, then chemical modification is carried out to graphite oxide by chloroactic acid method, obtains carboxylic
Base graphene oxide：Graphite oxide is added in deionized water first and ultrasonic disperse 2h obtains the oxidation that concentration is 4mg/mL
Graphene dispersing solution, then adds sodium hydroxide and monoxone ultrasonic disperse 4h, and by quality % ratios, wherein graphite oxide accounts for 0.5,
Sodium hydroxide 48.5, monoxone account for 51, and solution is repeatedly finally washed to supercentrifuge is in neutrality, and grinding is dried at 60 DEG C and is
Obtain carboxylated graphene oxide.
The preparation of amination graphene oxide：
Graphite oxide is made according to the method described above, then amination graphene oxide is prepared by chemical modification：First will
200mg graphite oxides add 400mL solvent dimethylformamides and ultrasound 1h obtains the oxidation that concentration is 2mg/mL at 30 DEG C
Graphene dispersing solution, then adds 300mg hexamethylene diamines and ultrasound and mechanical agitation 2h.Gained mixed liquor is transferred to water bath device
And add 13mg 2- (7- azos benzotriazole)-N, N, N', N'- tetramethylurea hexafluorophosphoric acid ester coupling agents, at 60 DEG C
Condensing reflux reacts 10h, and after the completion of reaction, with ethanol washed product 10 times, filtration product is placed in vacuum drying chamber 50 DEG C
Lower dry 12h is up to amination graphene oxide.
Embodiment 1
In-situ inserted solution method prepares carboxylated graphene oxide enhancing main chain benzoxazine/hydrocarbon resin bielement nano and answers
Resin：
The carboxylated graphene oxide of preparation is scattered in solvent dimethylformamide, is ultrasonically treated through power 600W
30min obtains 0.5g/L carboxylated graphene oxide solutions.By mass parts, by 15 parts of DDM type main chain benzoxazine prepolymers and 5
Part polybutadiene is dissolved in 80 parts of solvent dimethylformamides and is sufficiently stirred dissolving, obtains main chain benzoxazine/hydrocarbon
Resin prepolymer liquid solution.Carboxylated graphene oxide solution and main chain benzoxazine/hydrocarbon resin prepolymer solution are blended
To mixed liquor, by quality % ratios so that carboxylated graphene oxide and main chain benzoxazine/hydrocarbon resin performed polymer in mixed liquor
Mass ratio is 3:97.
Using in-situ inserted solution polymerization process, mixed liquor is reacted into 6h at 120 DEG C, then at 220 DEG C of curing reaction 10h,
Carboxylated graphene oxide enhancing main chain benzoxazine/hydrocarbon resin bielement nano compound resin is made.Its solidification temperature is
235 DEG C, glass transition temperature is 290 DEG C, tensile strength 168MPa, and the dielectric constant under 10GHz is 2.3, dielectric damage
Consume for 0.004.
Embodiment 2
In-situ inserted solution method prepares graphene oxide enhancing main chain benzoxazine/compound tree of hydrocarbon resin bielement nano
Fat：
The graphene oxide of preparation is scattered in Isosorbide-5-Nitrae-dioxane solvent, being ultrasonically treated 30min through power 800W obtains
To 1g/L graphene oxide solutions.By mass parts, by 15 parts of ODA type main chain benzoxazine prepolymers and 5 parts of styrene-maleic acids
Acid anhydride is dissolved in 80 parts of Isosorbide-5-Nitrae-dioxane solvents and is sufficiently stirred dissolving, and it is molten to obtain main chain benzoxazine/hydrocarbon resin performed polymer
Liquid.Amination graphene oxide solution and main chain benzoxazine/hydrocarbon resin prepolymer solution are blended to obtain mixed liquor, by matter
Measure % ratios so that graphene oxide and main chain benzoxazine/hydrocarbon resin performed polymer quality ratio are 5 in mixed liquor:95.
Using in-situ inserted solution polymerization process, mixed liquor is reacted into 8h at 90 DEG C, then at 180 DEG C of curing reaction 24h, system
Obtain graphene oxide enhancing main chain benzoxazine/hydrocarbon resin bielement nano compound resin.Its solidification temperature is 225 DEG C, glass
It is 295 DEG C, tensile strength 175MPa to change transition temperature, and the dielectric constant under 10GHz is 2.3, dielectric loss 0.005.
Embodiment 3
In-situ inserted solution method prepares amination graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary
Nanocomposite：
The amination graphene oxide of preparation is scattered in solvent dimethylformamide, is ultrasonically treated through power 800W
10min obtains 2g/L ammoxidation graphene solutions.By mass parts, by 5 parts of ODA type main chains benzoxazines, 2 parts of bisphenol-A phenolic aldehyde rings
Oxygen tree fat and 3 parts of styrene-butadiene copolymer are dissolved in 90 parts of solvent dimethylformamides and are sufficiently stirred dissolving, are led
Chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution, by amination graphene oxide solution and main chain benzoxazine/epoxy/
Hydrocarbon resin prepolymer solution is blended to obtain mixed liquor, by quality % ratios so that amination graphene oxide and master in mixed liquor
Chain benzoxazine/epoxy/hydrocarbon resin performed polymer quality ratio is 1:99.
Using in-situ inserted solution polymerization process, mixed liquor is reacted into 2h at 140 DEG C, then at 220 DEG C of curing reaction 10h,
Amination graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary nano compound resin is made.Its solidification temperature
For 225 DEG C, glass transition temperature is 312 DEG C, tensile strength 185MPa, and the dielectric constant under 10GHz is 2.2, dielectric
It is lost as 0.003.
Embodiment 4
In-situ inserted solution method prepares carboxylated graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary
Nanocomposite：
The carboxylated graphene oxide of preparation is scattered in toluene solvant, being ultrasonically treated 30min through power 400W obtains
3g/L carboxylated graphene oxide solutions.By mass parts, by 8 parts of DDM type main chains benzoxazines, 1 part of dicyclopentadiene asphalt mixtures modified by epoxy resin
Fat and 1 part of styrene-butadiene copolymer are dissolved in 90 parts of toluene solvants and are sufficiently stirred dissolving, obtain main chain benzoxazine/
Epoxy/hydrocarbon resin prepolymer solution.Carboxylated graphene oxide solution and main chain benzoxazine/epoxy/hydrocarbon resin is pre-
Oligomer solution is blended to obtain mixed liquor, by quality % ratios so that and carboxylated graphene oxide and main chain benzoxazine in mixed liquor/
Epoxy/hydrocarbon resin performed polymer quality ratio is 1:99.
Using in-situ inserted solution polymerization process, mixed liquor is reacted into 6h at 110 DEG C, then at 180 DEG C of curing reaction 22h,
Carboxylated graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary nano compound resin is made.Its solidification temperature
For 235 DEG C, glass transition temperature is 325 DEG C, tensile strength 178MPa, and the dielectric constant under 10GHz is 2.1, dielectric
It is lost as 0.002.
Embodiment 5
In-situ inserted solution method prepares carboxylated graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary
Nanocomposite：
The carboxylated graphene oxide of preparation is scattered in toluene/ethanol solvent (toluene：Ethanol volume ratio=1:2) in,
30min, which is ultrasonically treated, through power 400W obtains 3g/L carboxylated graphene oxide solutions.By mass parts, by 15 parts of ODA type main chains
Benzoxazine, 2 parts of bisphenol A epoxide resins, 3 parts of glycidyl ester type epoxy resins and 10 parts of styrene-isoprene copolymerization
Thing is dissolved in 70 parts of toluene/ethanol solvent (toluene：Ethanol volume ratio=1:2) in and dissolving is sufficiently stirred, obtains main chain Ben Bing Evil
Piperazine/epoxy/hydrocarbon resin prepolymer solution.By carboxylated graphene oxide solution and main chain benzoxazine/epoxy/hydrocarbon tree
Fat prepolymer solution is blended to obtain mixed liquor, by quality % ratios, carboxylated graphene oxide and main chain benzoxazine/epoxy/carbon
Hydrogen resin prepolymer body mass ratio is 3:97.
Using in-situ inserted solution polymerization process, mixed liquor is reacted into 8h at 90 DEG C, then at 170 DEG C of curing reaction 24h, system
Obtain carboxylated graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary nano compound resin.Its solidification temperature is
227 DEG C, glass transition temperature is 350 DEG C, tensile strength 188MPa, and the dielectric constant under 10GHz is 1.2, dielectric damage
Consume for 0.001.
Embodiment 6
In-situ inserted solution method prepares carboxylated graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary
Nanocomposite：
The carboxylated graphene oxide of preparation is scattered in toluene/ethanol solvent (toluene：Ethanol volume ratio=2:1) in,
30min, which is ultrasonically treated, through power 400W obtains 3g/L carboxylated graphene oxide solutions.By mass parts, by 15 parts of DDM type main chains
Benzoxazine prepolymer, 5 parts of paraxylene epoxy resin, 2 parts of phenylethylene-maleic anhydrides, 4 parts of styrene-butadiene copolymer
And 4 parts of polybutadienes are dissolved in 70 parts of toluene/ethanol solvent (toluene：Ethanol volume ratio=2:1) in and it is sufficiently stirred molten
Solution, obtains main chain benzoxazine/epoxy/hydrocarbon resin prepolymer solution.By carboxylated graphene oxide solution and main chain benzo
Oxazine/epoxy/hydrocarbon resin prepolymer solution is blended to obtain mixed liquor, by quality % ratios so that carboxylated aoxidizes in mixed liquor
Graphene is 5 with main chain benzoxazine/epoxy/hydrocarbon resin performed polymer quality ratio:95.
Using in-situ inserted solution polymerization process, mixed liquor is reacted into 6h at 80 DEG C, then at 220 DEG C of curing reaction 10h, system
Obtain carboxylated graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary nano compound resin.Its solidification temperature is
228 DEG C, glass transition temperature is 325 DEG C, tensile strength 190MPa, and the dielectric constant under 10GHz is 1.6, dielectric damage
Consume for 0.002.
Embodiment 7
In-situ inserted solution method prepares amination graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary
Nanocomposite：
The amination graphene oxide of preparation is scattered in chloroform solvent, 30min is ultrasonically treated through power 600W
Obtain 10g/L amination graphene oxide solutions.By mass parts, by 6 parts of ODA type main chains benzoxazines, 2 parts of dicyclopentadiene rings
Oxygen tree fat and 2 parts of styrene-isoprene copolymers are dissolved in 90 parts of chloroform solvents and are sufficiently stirred dissolving, obtain main chain
Benzoxazine/epoxy/hydrocarbon resin prepolymer solution.By amination graphene oxide solution and main chain benzoxazine/epoxy/carbon
Hydrogen resin prepolymer solution blending obtains mixed liquor, by quality % ratios so that amination graphene oxide and main chain in mixed liquor
Benzoxazine/epoxy/hydrocarbon resin performed polymer quality ratio is 5:90.
Using in-situ inserted solution polymerization process, mixed liquor is reacted into 7h at 80 DEG C, then at 220 DEG C of curing reaction 10h, system
Obtain amination graphene oxide enhancing main chain benzoxazine/epoxy/hydrocarbon resin ternary nano compound resin.Its solidification temperature is
226 DEG C, glass transition temperature is 345 DEG C, tensile strength 189MPa, and the dielectric constant under 10GHz is 1.8, dielectric damage
Consume for 0.002.
Claims (7)
1. graphene oxide enhancing main chain benzoxazine compound resin can be changed, it is characterised in that：It is functional graphene oxide
Modified main chain benzoxazine/hydrocarbon resin binary resin, or functional graphene oxide are modified main chain benzoxazine/asphalt mixtures modified by epoxy resin
Fat/hydrocarbon resin ternary resin, by weight 0.1~5 part of functional graphene oxide, main chain benzoxazine/hydrocarbon resin
Binary resin or main chain benzoxazine/epoxy resin/5~99.9 parts of hydrocarbon resin ternary resin；The functionalization oxidation stone
Black alkene is carboxylated graphene oxide or amination graphene oxide；
The main chain benzoxazine/hydrocarbon resin binary resin is by 50~90 parts by weight of main chain benzoxazine and hydrocarbon resin 10
The main chain benzoxazine that~50 parts by weight cross-linked polymerics obtain/hydrocarbon resin binary performed polymer cures；The main chain
Benzoxazine/epoxy resin/hydrocarbon resin ternary resin is by 50~80 parts by weight of main chain benzoxazine；10~20 weight of epoxy resin
Measure part；Main chain benzoxazine/epoxy resin/hydrocarbon resin ternary polymerization that 10~30 parts by weight cross-linked polymeric of hydrocarbon resin obtains
What system cured.
2. functional graphene oxide according to claim 1 strengthens main chain benzoxazine compound resin, it is characterised in that：
Main chain benzoxazine of the present invention has with lower structure：
For DDM type main chain benzoxazines,
OrFor ODA type main chain benzoxazines.
Wherein n=2.5~20.
3. functional graphene oxide according to claim 1 strengthens main chain benzoxazine compound resin, it is characterised in that：
The epoxy resin is following one of which or its combination：Bisphenol A epoxide resin, bisphenol F epoxy resin, bisphenol-s epoxy resin,
Novolac epoxy resin, bisphenol-A phenolic epoxy resin, bisphenol F phenolic epoxy resin, o-cresol epoxy resin, trifunctional epoxy
Resin, four-functional group epoxy resin, polyfunctional epoxy resin, DCPD-containing epoxy resin, paraxylene epoxy resin, naphthalene
Type epoxy resin, biphenyl novolac epoxy resin, isocyanate modified epoxy resin and phenol benzaldehyde epoxy resin；The hydrocarbon tree
Fat is following one of which or its combination：Polybutadiene, butadiene styrene resin, phenylethylene-maleic anhydride, styrene-butadiene
Copolymer, cyclic olefin copolymer, styrene-isoprene copolymer, polyisoprene rubber, styrene-butadiene-diethyl
Alkenyl benzene copolymer, hydrogenated diene-butadiene-styrene copolymer.
4. functional graphene oxide according to claim 1 strengthens main chain benzoxazine compound resin, it is characterised in that：
The carboxylated graphene oxide is the graphene oxide that is effectively peeled off by graphite oxide ultrasonic disperse in alcohol solvent
Solution, carries out chemical modification to graphene oxide solution by chloroactic acid method and obtains；The ultrasonic disperse is in ice-water bath condition
Lower ultrasonic 10~30min, ultrasonic power are 400~800W；
The amination graphene oxide obtains to add graphene oxide into solvent dimethylformamide through ultrasonic disperse
The graphene oxide dispersion of 1~4mg/mL, then adds diamine monomer, wherein diamine monomer and oxidation stone into the dispersion liquid
The mass ratio of ink is 1.5~3：1, it is sufficiently mixed and uniformly adds coupling agent afterwards, the mass ratio of coupling agent and graphite oxide is 5~8:
100, and in 50~70 DEG C of 6~10h of back flow reaction, products therefrom is washed with ethanol, filtered, is dried to obtain after reaction；Institute
The graphene oxide stated is using natural flake graphite as raw material, and graphite oxide is made by improved Hummers methods.The day
Right crystalline flake graphite particle diameter is 30~40 μm.
5. the in-situ inserted solution system of the functional graphene oxide enhancing main chain benzoxazine compound resin described in claim 1
Preparation Method, step are：Functional graphene oxide is scattered in organic solvent by ultra-sonic dispersion method, obtain 0.1~
The functional graphene oxide uniform dispersion of 10g/L；Main chain benzoxazine binary or ternary resin prepolymer are dissolved in accordingly
In organic solvent, the prepolymer solution that mass concentration is 10~30% is obtained；
Functional graphene oxide dispersion liquid and prepolymer solution are carried out blending to be uniformly mixed liquid so that oxygen in mixed liquor
Graphite alkene or functional graphene oxide and main chain benzoxazine binary or ternary resin performed polymer quality ratio are 0.1~1：99
~99.9；
Gained mixed liquor is reacted into 2~8h at 80~140 DEG C, then at 100~220 DEG C of 4~24h of curing reaction, obtains function
Change graphene oxide enhancing main chain benzoxazine compound resin.
6. according to the method described in claim 5, it is characterized in that：Organic solvent of the present invention is acetone, toluene, diformazan
The mixture of any one or more in benzene, ethanol, chloroform, dimethylformamide, Isosorbide-5-Nitrae-dioxane.
7. the functional graphene oxide described in claim 1 strengthens main chain benzoxazine compound resin as high-frequency electromagnetic wave
Under the conditions of low dielectric, low-loss material application.
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| CN110885419A (en) * | 2019-10-18 | 2020-03-17 | 淮北绿洲新材料有限责任公司 | Ultrahigh-frequency low-dielectric-property carboxylated graphene reinforced poly (benzoxazine-urethane) nano composite resin and preparation method thereof |
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| CN114230787A (en) * | 2021-12-13 | 2022-03-25 | 南亚新材料科技股份有限公司 | Modified benzoxazine prepolymer, preparation method thereof, resin composition, cured product thereof and electronic product component |
| CN115368142A (en) * | 2022-07-28 | 2022-11-22 | 杭州大和江东新材料科技有限公司 | Low dielectric loss aluminum nitride ceramic material and preparation method thereof |
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