CN108250749A - A kind of preparation method of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film - Google Patents
A kind of preparation method of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film Download PDFInfo
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Abstract
A kind of preparation method of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film, the present invention relates to insulating materials technical fields, and in particular to a kind of preparation method of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film.The problem of its thermal property and mechanical property being improved while can not taking into account the present invention is to solve existing laminated film and reduce dielectric constant.Method：Graphene oxide is prepared by improved Hummers methods；Phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film is prepared using situ aggregation method.The present invention is applied to the preparation of phenyl silsesquioxane/graphene oxide/polyimides three-phase film.
Description
Technical field
The present invention relates to insulating materials technical fields, and in particular to a kind of phenyl silsesquioxane/graphene oxide/polyamides
The preparation method of imines three-phase composite film.
Background technology
In recent years, application of the nano-porous materials with low-k in microelectronics industry causes great pass
Note.Due to good mechanical property, hot property and electrical property, polyimides has been widely used for microelectronics industry dielectric material
And packaging material.However, the continuous reduction of the characteristic size with integrated circuit chips, the resistance and capacitance of interconnection parasitic are just
The delay, crosstalk and energy loss of signal transmission can be caused, this become integrated circuit to high speed, high density, low energy consumption and
The new yoke of multifunctional direction development.In order to reach the requirement of integrated circuit high integration, the transmission speed of signal is improved, is sealed
Highdensity signal line requirement in dress remains electrically isolated from each other, should choose the alap material conduct of dielectric constant
The insulating materials of metal interlevel can be transmitted normally with the electric interactive signal for ensuring minimum in adjacent circuit.Utilize air
Low-k can be substantially reduced the dielectric constant of polyimides, a kind of method be by introduce in the base gap prepare it is low
Dielectric material, another method are to reduce material in polyimides to introduce the monomer with hollow-core construction in a manner of hydridization
The dielectric constant of material.There is nano-scale, uniform, blind bore gap to be conducive to keep its electricity and mechanical property in material.Cause
This, the air gap is introduced in connection structure material and introduces air in the polymer to have reduced the dielectric constant of material
As an attracting method.
The Kapton of low-k is prepared, can be realized by introducing inorganic component, a kind of inorganic-organic group
Point-phenyl oligomeric silsesquioxane is by rigid cube silica [octamer (R8Si8O12)] core is with size
The hole composition of 0.3~0.4nm.With the special construction between inorganic ceramic and organic osmanthus polymer, thus it is this kind of
Molecule has hydridization property.Thin polymer film based on phenyl silsesquioxane has low-k property, in preparation process
It adds coupling agent modified phenyl silsesquioxane and introduces polyimides, the organic-inorganic hybrid nanocomposite object of preparation has than original
The lower dielectric constant of polyimides.Another kind of inorganic component-graphene oxide, with expensive fullerene and carbon nanotube phase
Than graphene oxide is cheap, and raw material is easy to get, the nano-lamellar structure having had, large specific surface area, the abundant function in surface
Group etc. makes it have preferable dispersibility in water and organic solvent, and chemical bond or hydrogen bond are formed easily between polymer, so as to
Make it that conveniently there are the potentiality of bigger, especially mechanical property and warm blood performance in the properties for improving polymer composites
Raising in terms of, therefore available for polymer nano composite film preparation.It is but phenyl silsesquioxane is same with graphene oxide
When introduce polyimide matrix among modified synergic research it is relatively fewer.Therefore, it prepares with low-k and good
Phenyl silsesquioxane/graphene oxide of good comprehensive performance/polyimides three-phase composite film has very important significance.
Invention content
The present invention is to solve existing laminated film can not take into account reduce dielectric constant while improve its thermal property and
The problem of mechanical property, and a kind of preparation of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film is provided
Method.
A kind of preparation method of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film of the present invention is
It carries out according to the following steps：
First, under the conditions of ice-water bath, expanded graphite is dissolved using mixed acid solution, mechanical agitation is completely molten to expanded graphite
Solution, then adds in potassium permanganate, mechanical agitation continues 1~2h of stirring, then shifts after being completely dissolved to potassium permanganate thereto
1~2h is kept the temperature into the water-bath that temperature is 35 DEG C, the temperature of water-bath is then warming up to 98 DEG C from 35 DEG C, in temperature-rise period
Middle using separatory funnel, at the uniform velocity addition deionized water to temperature reaches 98 DEG C thereto, and 1 is kept the temperature under conditions of being 98 DEG C in temperature
After~2h, hydrogenperoxide steam generator to the solution for adding in a concentration of 30% becomes glassy yellow；Bright yellow solution is diluted, is filtered
Reaction product, it is 7 that obtained liquid, which is centrifuged repeatedly to pH value, and the product of gained is dried and ground, obtains graphite oxide powder
The graphite oxide powder prepared is added in deionized water, is dried after ultrasonic vibration 3h, obtain graphene oxide by body；It is described
Mixed acid solution is concentrated nitric acid and the concentrated sulfuric acid by volume 1:3 are mixed to get；The quality of the expanded graphite and mixed acid solution
Volume ratio is 1g:(80~120) mL；The mass ratio of the expanded graphite and potassium permanganate is 1:(5~7)；The expanded graphite
Quality and temperature-rise period in the volume ratio of deionized water that at the uniform velocity adds in be 1g:(180~220) mL；
2nd, N is added in the graphene oxide obtained into step 1, N '-dimethyl acetamide solution, ultrasonic disperse is equal
It is even, obtain dispersion liquid；Dispersion liquid is transferred in thermostat water bath, to dispersion under conditions of temperature is 60 DEG C and nitrogen protection
4,4 '-diaminodiphenyl ether I is added in liquid, is refluxed 20~28h, then first adds in phenyl silsesquioxane thereto, is surpassed
Sound adds silane coupling agent after being uniformly dispersed, and continues stirring to after mixing, adding in 4,4 '-diaminodiphenyl ether II again
And pyromellitic acid anhydride, 12h is stirred at room temperature, it is molten to obtain nanometer phenyl silsesquioxane/graphene oxide/polyamic acid
Liquid；The mass ratio of graphene oxide and 4,4 '-diaminodiphenyl ether I is 2:3；The additive amount of graphene oxide is 4,4 '-diamino
The 0.1%~0.9% of yl diphenyl ether II and pyromellitic acid anhydride gross mass；The additive amount of phenyl silsesquioxane for 4,4 '-
The 1%~3% of diaminodiphenyl ether II and pyromellitic acid anhydride gross mass；The quality of the 4,4 '-diaminodiphenyl ether II
With N, the volume ratio of N '-dimethyl acetamide solution is 1g:12mL；4,4 '-diaminodiphenyl ether II and pyromellitic acid anhydride
Molar ratio be 99:100；
3rd, the nanometer phenyl silsesquioxane/graphene oxide/polyamic acid solution obtained step 2 is transferred to temperature
After heating degradation 30min in 50 DEG C of thermostat water baths, plastic film mulch processing is carried out, is then heated to by the way of gradient increased temperature
300 DEG C of progress hot imidizations, are cooled to room temperature, obtain POSS/ODA-GO/PI laminated films.
The beneficial effects of the invention are as follows：
1st, present invention is mainly applied to the uses of field of microelectronics electronic package material, and phenyl is prepared using situ aggregation method
Silsesquioxane/graphene oxide/polyimides three-phase composite film prepares graphene oxide by improved Hummers methods.
By scanning electron microscope and atomic force microscope characterization result it is found that the graphene oxide layer is relatively thin, thickness in monolayer reaches
0.78nm。
It is 2nd, of the invention by the way that the phenyl silsesquioxane with rigid hollow kernel is carried in graphene oxide layer,
It is introduced into polyimide matrix that be prepared for a kind of dielectric properties, thermal property and mechanical property all good by situ aggregation method
Three-phase composite material, can be applied in field of microelectronics in circuit board and its encapsulating material.
3rd, the advantage of the invention is that used phenyl silsesquioxane is in nanoscale, nanometer can be given full play to
For grain to the enhancing effect of material, the graphene oxide layer is relatively thin, after being loaded with phenyl silsesquioxane, Neng Goujun
It is even to be scattered in polyimide matrix, and phenyl silsesquioxane/graphene oxide/polyimides three-phase composite material has
The features such as excellent dielectric properties, thermal property and mechanical property parameters；Its dielectric constant be 2.5-2.9 (1MHz), material
5wt% heat decomposition temperatures are 446~564 DEG C, and tensile strength is in 81.8~93.5MPa.
4th, nanoscale phenyl silsesquioxane of the invention is apparent special as a kind of novel organic and inorganic filler
Sign is exactly to have the kernel of hollow structure, and entire molecule is in nanoscale, the introducing meeting of nano level phenyl silsesquioxane
More air are introduced into matrix, so as to be substantially reduced its dielectric constant, and in the rigidity of phenyl silsesquioxane itself
Core imparts its good mechanical property, and higher heat decomposition temperature also makes it have good thermal property, with polyamides Asia
It disclosure satisfy that requirement of the high speed integrated circuit to dielectric material after amine is compound.
5th, graphene oxide of the invention is a kind of one of important derivative of graphene, and graphene oxide has because of it
High specific surface area, special graphite two-dimension plane structure and low processing cost and in the performance side for promoting polymer
Face has great application prospect application prospect.The foundation structure of graphene oxide is similar with graphene, so that graphene oxide has
Good physical property.But it is different from graphene in chemical constitution, therefore has the potentiality of further functionalization.It is aoxidizing
The sheet surfaces of graphene sheet layer and surrounding are connected to abundant oxygen-containing group, such as hydroxyl, carboxyl, epoxy group and carbonyl, these
The oxygen-containing group of surface of graphene oxide make it have good dielectric properties, multiple chemical functionalization basic points, preferably
Compatibility, and enable to form chemical bond by reacting between graphene oxide and polymer, enhance graphene oxide
Dispersibility in the polymer matrix.By into polymer adulterate graphene oxide be conducive to obtain thermal stability it is good,
The composite material of superior dielectric performance is provided simultaneously with, therefore graphene oxide is in the low dielectric composite wood for preparing excellent combination property
Huge effect is played in terms of material base material.
6th, the present invention uses nano level phenyl silsesquioxane, by silane coupling agent with using improved Hummers
Hair is prepared graphene oxide-loaded, and phenyl silsesquioxane/graphene oxide composite granule and polyamic acid is compound, is played
Phenyl silsesquioxane and graphene oxide are to the castering action of dielectric material performance, thermal property and mechanical property, through follow-up
It is sub- that phenyl silsesquioxane/graphene oxide with low-k, calorifics and good mechanical properties/polyamides is prepared in processing
Amine three-phase composite material.
Description of the drawings
Fig. 1 is the graphene oxide atomic force microscopy diagram that embodiment one obtains；
Fig. 2 is the transmission electron microscope picture of graphene oxide that embodiment one obtains；
Fig. 3 is the transmission electron microscope picture of 4,4 '-diaminodiphenyl ether-graphene oxide that embodiment one obtains；
Fig. 4 is the transmission electron microscope picture of nanometer phenyl silsesquioxane in embodiment one；
Fig. 5 is the powder transmission electron microscope picture that the nanometer phenyl silsesquioxane that embodiment one obtains loads graphene oxide；
Fig. 6 is the scanning electricity for phenyl silsesquioxane/graphene oxide/composite polyimide material that embodiment one obtains
Mirror figure.
Specific embodiment
Specific embodiment one：A kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase of present embodiment is answered
The preparation method for closing film is to carry out according to the following steps：
First, under the conditions of ice-water bath, expanded graphite is dissolved using mixed acid solution, mechanical agitation is completely molten to expanded graphite
Solution, then adds in potassium permanganate, mechanical agitation continues 1~2h of stirring, then shifts after being completely dissolved to potassium permanganate thereto
1~2h is kept the temperature into the water-bath that temperature is 35 DEG C, the temperature of water-bath is then warming up to 98 DEG C from 35 DEG C, in temperature-rise period
Middle using separatory funnel, at the uniform velocity addition deionized water to temperature reaches 98 DEG C thereto, and 1 is kept the temperature under conditions of being 98 DEG C in temperature
After~2h, hydrogenperoxide steam generator to the solution for adding in a concentration of 30% becomes glassy yellow；Bright yellow solution is diluted, is filtered
Reaction product, it is 7 that obtained liquid, which is centrifuged repeatedly to pH value, and the product of gained is dried and ground, obtains graphite oxide powder
The graphite oxide powder prepared is added in deionized water, is dried after ultrasonic vibration 3h, obtain graphene oxide by body；It is described
Mixed acid solution is concentrated nitric acid and the concentrated sulfuric acid by volume 1:3 are mixed to get；The quality of the expanded graphite and mixed acid solution
Volume ratio is 1g:(80~120) mL；The mass ratio of the expanded graphite and potassium permanganate is 1:(5~7)；The expanded graphite
Quality and temperature-rise period in the volume ratio of deionized water that at the uniform velocity adds in be 1g:(180~220) mL；
2nd, N is added in the graphene oxide obtained into step 1, N '-dimethyl acetamide solution, ultrasonic disperse is equal
It is even, obtain dispersion liquid；Dispersion liquid is transferred in thermostat water bath, to dispersion under conditions of temperature is 60 DEG C and nitrogen protection
4,4 '-diaminodiphenyl ether I is added in liquid, is refluxed 20~28h, then first adds in phenyl silsesquioxane thereto, is surpassed
Sound adds silane coupling agent after being uniformly dispersed, and continues stirring to after mixing, adding in 4,4 '-diaminodiphenyl ether II again
And pyromellitic acid anhydride, 12h is stirred at room temperature, it is molten to obtain nanometer phenyl silsesquioxane/graphene oxide/polyamic acid
Liquid；The mass ratio of graphene oxide and 4,4 '-diaminodiphenyl ether I is 2:3；The additive amount of graphene oxide is 4,4 '-diamino
The 0.1%~0.9% of yl diphenyl ether II and pyromellitic acid anhydride gross mass；The additive amount of phenyl silsesquioxane for 4,4 '-
The 1%~3% of diaminodiphenyl ether II and pyromellitic acid anhydride gross mass；The quality of the 4,4 '-diaminodiphenyl ether II
With N, the volume ratio of N '-dimethyl acetamide solution is 1g:12mL；4,4 '-diaminodiphenyl ether II and pyromellitic acid anhydride
Molar ratio be 99:100；
3rd, the nanometer phenyl silsesquioxane/graphene oxide/polyamic acid solution obtained step 2 is transferred to temperature
After heating degradation 30min in 50 DEG C of thermostat water baths, plastic film mulch processing is carried out, is then heated to by the way of gradient increased temperature
300 DEG C of progress hot imidizations, are cooled to room temperature, obtain POSS/ODA-GO/PI laminated films.
Phenyl silsesquioxane and graphene oxide are uniformly distributed in polyamides Asia by present embodiment by situ aggregation method
In amido body, graphene oxide is modified through 4,4 '-diaminodiphenyl ether, and the interlamellar spacing of graphene oxide layer further increases
Add, be conducive to form chemical bond between graphene oxide and polyimide matrix, be conducive to graphene oxide in recombination process
It is uniformly distributed, and phenyl silsesquioxane is carried on the surface of graphene oxide, it is same along with being uniformly distributed for graphene oxide
Sample is uniformly distributed in polyimide matrix, be conducive to be uniformly distributed and performance stablize three-phase composite film.Described
Phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film contributes to the reduction of polymide dielectric constant simultaneously
Keep its thermal property and mechanical property.Phenyl silsesquioxane/the graphene oxide/polyimides three-phase composite film
The performance of composite polyimide material can be changed by adjusting the tret of phenyl silsesquioxane and graphene oxide.
It is added in present embodiment step 2 after 4,4 '-diaminodiphenyl ether II and pyromellitic acid anhydride when the two mole
When ratio reaches equivalent, system viscosity increased dramatically, and apparent rod climbing phenomenon occurs,
Specific embodiment two：The present embodiment is different from the first embodiment in that：Stone is expanded described in step 1
The quality of ink and the volume ratio of mixed acid solution are 1g:100mL.It is other same as the specific embodiment one.
Specific embodiment three：The present embodiment is different from the first and the second embodiment in that：It is swollen described in step 1
The mass ratio of swollen graphite and potassium permanganate is 1:6.It is other the same as one or two specific embodiments.
Specific embodiment four：Present embodiment is unlike specific embodiment one to three：It is high described in step 1
The feed postition of potassium manganate is as follows：Potassium permanganate average mark is added for 6 times, per minor tick 10min.Other and specific embodiment
One to three is identical.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Institute in step 1
State expanded graphite quality and temperature-rise period in the volume ratio of deionized water that at the uniform velocity adds in be 1g:200mL.Other and specific reality
It is identical to apply one of mode one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to five：Institute in step 2
Silane coupling agent is stated as 3- aminopropyl trimethoxysilanes, often adds 4,4 '-diaminodiphenyl ether II and pyromellitic acid anhydride
1% phenyl silsesquioxane of gross mass, 5 drop silane coupling agent of addition.It is other identical with one of specific embodiment one to five.
The silane coupling agent is titrated using normal burette.
Specific embodiment seven：Unlike one of present embodiment and specific embodiment one to six：Institute in step 2
The feed postition for stating pyromellitic acid anhydride is as follows：Pyromellitic acid anhydride average mark is added for 6 times, per minor tick 15min.Its
One of it and specific embodiment one to six are identical.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：Institute in step 2
State the additive amount of graphene oxide for 4,4 '-diaminodiphenyl ether II and pyromellitic acid anhydride gross mass 0.1%~
0.9%.It is other identical with one of specific embodiment one to seven.
Specific embodiment nine：Unlike one of present embodiment and specific embodiment one to eight：Institute in step 3
It is that temperature is warming up to 80 DEG C from 50 DEG C to state gradient increased temperature, and 0.5h is kept under conditions of being 80 DEG C in temperature, then by temperature by
80 DEG C are warming up to 120 DEG C, and keep 0.5h under conditions of being 120 DEG C in temperature, and temperature then is warming up to 150 DEG C by 120 DEG C,
0.5h is kept, then temperature is warming up to 180 DEG C by 150 DEG C under conditions of being 150 DEG C in temperature, in the condition that temperature is 180 DEG C
Lower holding 0.5h, then temperature is warming up to 200 DEG C by 180 DEG C, keep 0.5h under conditions of being 200 DEG C in temperature.Again by temperature
250 DEG C are warming up to by 200 DEG C, 0.5h is kept under conditions of being 250 DEG C in temperature.Temperature is warming up to 300 DEG C by 250 DEG C again,
0.5h is kept under conditions of being 300 DEG C in temperature.It is other identical with one of specific embodiment one to eight.
Beneficial effects of the present invention are verified by following embodiment：
Embodiment one：A kind of preparation method of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film
It is to carry out according to the following steps：
First, under the conditions of ice-water bath, 1g expanded graphites are dissolved using mixed acid solution, mechanical agitation is completely molten to expanded graphite
Solution, then adds in 6g potassium permanganate thereto, and mechanical agitation continues to stir 1h after being completely dissolved to potassium permanganate, be then transferred to
Temperature is to keep the temperature 2h in 35 DEG C of water-bath, and the temperature of water-bath then is warming up to 98 DEG C from 35 DEG C, is adopted in temperature-rise period
It at the uniform velocity adds in 200mL deionized waters to temperature thereto with separatory funnel and reaches 98 DEG C, kept the temperature under conditions of being 98 DEG C in temperature
After 1h, hydrogenperoxide steam generator to the solution for adding in a concentration of 30% becomes glassy yellow；Bright yellow solution is diluted, filtering is anti-
Product is answered, it is 7 that obtained liquid, which is centrifuged repeatedly to pH value, and the product of gained is dried and ground, obtains graphite oxide powder,
The graphite oxide powder prepared is added in deionized water, is dried after ultrasonic vibration 3h, obtains graphene oxide；The nitration mixture
Solution is mixed to get for 25mL concentrated nitric acids with the 75mL concentrated sulfuric acids；The feed postition of the potassium permanganate is as follows：By potassium permanganate
Average mark adds for 6 times, per minor tick 10min；
2nd, N is added in the graphene oxide obtained into step 1, N '-dimethyl acetamide solution, ultrasonic disperse is equal
It is even, obtain dispersion liquid；Dispersion liquid is transferred in thermostat water bath, to dispersion under conditions of temperature is 60 DEG C and nitrogen protection
4,4 '-diaminodiphenyl ether I is added in liquid, is refluxed 20~28h, then first adds in phenyl silsesquioxane thereto, is surpassed
Sound adds silane coupling agent after being uniformly dispersed, and continues stirring to after mixing, adding in 4,4 '-diaminodiphenyl ether II again
And pyromellitic acid anhydride, 12h is stirred at room temperature, it is molten to obtain nanometer phenyl silsesquioxane/graphene oxide/polyamic acid
Liquid；The mass ratio of graphene oxide and 4,4 '-diaminodiphenyl ether II is 2:3；The additive amount of graphene oxide is 4,4 '-diamino
The 0.1%~0.9% of yl diphenyl ether II and pyromellitic acid anhydride gross mass；The additive amount of phenyl silsesquioxane for 4,4 '-
The 1%~3% of diaminodiphenyl ether II and pyromellitic acid anhydride gross mass；The quality of the 4,4 '-diaminodiphenyl ether II
With N, the volume ratio of N '-dimethyl acetamide solution is 1g:12mL；4,4 '-diaminodiphenyl ether II and pyromellitic acid anhydride
Molar ratio be 99:100；The feed postition of the pyromellitic acid anhydride is as follows：By 6 throwings of pyromellitic acid anhydride average mark
Add, per minor tick 15min；
3rd, the nanometer phenyl silsesquioxane/graphene oxide/polyamic acid solution obtained step 2 is transferred to temperature
After heating degradation 30min in 50 DEG C of thermostat water baths, plastic film mulch processing is carried out, is then heated to by the way of gradient increased temperature
300 DEG C of progress hot imidizations, are cooled to room temperature, obtain POSS/ODA-GO/PI laminated films；The gradient increased temperature is will be warm
Degree is warming up to 80 DEG C from 50 DEG C, and keeps 0.5h, then temperature is warming up to 120 DEG C by 80 DEG C under conditions of being 80 DEG C in temperature,
And temperature is then warming up to 150 DEG C by 120 DEG C, is 150 DEG C in temperature to keep 0.5h under conditions of 120 DEG C in temperature
Under the conditions of keep 0.5h, then temperature is warming up to 180 DEG C by 150 DEG C, in temperature to keep 0.5h under conditions of 180 DEG C, then will
Temperature is warming up to 200 DEG C by 180 DEG C, and 0.5h is kept under conditions of being 200 DEG C in temperature.Temperature is warming up to 250 by 200 DEG C again
DEG C, keep 0.5h under conditions of being 250 DEG C in temperature.Temperature is warming up to 300 DEG C by 250 DEG C again, in the item that temperature is 300 DEG C
0.5h is kept under part.
Fig. 1 is the graphene oxide atomic force microscopy diagram that embodiment one obtains；Fig. 2 is the oxidation stone that embodiment one obtains
The transmission electron microscope picture of black alkene；Fig. 3 is the transmission electron microscope picture of 4,4 '-diaminodiphenyl ether-graphene oxide that embodiment one obtains；
Fig. 4 is the transmission electron microscope picture of nanometer phenyl silsesquioxane in embodiment one；Fig. 5 is the nanometer phenyl sesquialter that embodiment one obtains
Siloxanes loads the powder transmission electron microscope picture of graphene oxide；Fig. 6 is phenyl silsesquioxane/oxidation stone that embodiment one obtains
The scanning electron microscope (SEM) photograph of black alkene/composite polyimide material.
The thickness measured in Fig. 1 between 2 points is 0.78nm, illustrates that graphene oxide layer prepared by the present invention is relatively thin, single
Layer reaches Nano grade.
From Fig. 2 can find out that the lamella edge length of graphene oxide of the invention prepared is 500nm to 1 μm.
From Fig. 3 it can be seen that by 4, the modified graphene oxide layer of 4 '-diaminodiphenyl ether, surface folding increases
Add, illustrate to be modified successfully and piece interfloor distance increases due to modification.
From Fig. 4 it can be seen that the phenyl silsesquioxane filler surface size that uses of the present invention for the length of side be 10~20nm it
Between cube structure, illustrate that the phenyl silsesquioxane that uses of the present invention is in nano-scale, Nano filling pair can be played
The enhancing effect of material.
From Fig. 5 it can be seen that phenyl silsesquioxane particulate load illustrates companion in graphene oxide layer surface and surrounding
As graphene oxide is uniformly distributed in polyimide matrix, phenyl silsesquioxane can also be uniformly distributed in polyimide-based
In body.
From Fig. 6 it can be seen that material section is evident that graphene oxide layer, and clearly visible it is uniformly distributed
Phenyl silsesquioxane particle, it is polyimide-based to illustrate that graphene oxide layer is uniformly wrapped on phenyl silsesquioxane
Internal portion can give full play to enhancing effect of the filler to basis material.
Claims (9)
1. a kind of preparation method of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film, it is characterised in that
The preparation method of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film is to carry out according to the following steps：
First, under the conditions of ice-water bath, expanded graphite is dissolved using mixed acid solution, mechanical agitation to expanded graphite is completely dissolved, so
Add in potassium permanganate thereto afterwards, mechanical agitation continues 1~2h of stirring, is then transferred to temperature after being completely dissolved to potassium permanganate
To keep the temperature 1~2h in 35 DEG C of water-baths, the temperature of water-bath is then warming up to 98 DEG C from 35 DEG C, is used in temperature-rise period
Separatory funnel at the uniform velocity adds in deionized water to temperature and reaches 98 DEG C thereto, under conditions of being 98 DEG C in temperature after 1~2h of heat preservation,
Hydrogenperoxide steam generator to the solution for adding in a concentration of 30% becomes glassy yellow；Bright yellow solution is diluted, filtering reaction production
Object, it is 7 that obtained liquid, which is centrifuged repeatedly to pH value, and the product of gained is dried and ground, obtains graphite oxide powder, will be made
The graphite oxide powder got ready is added in deionized water, is dried after ultrasonic vibration 3h, is obtained graphene oxide；The mixed acid solution
For concentrated nitric acid and the concentrated sulfuric acid by volume 1:3 are mixed to get；The quality of the expanded graphite and the volume ratio of mixed acid solution are
1g:(80~120) mL；The mass ratio of the expanded graphite and potassium permanganate is 1:(5~7)；The quality of the expanded graphite with
The volume ratio of the deionized water at the uniform velocity added in temperature-rise period is 1g:(180~220) mL；
2nd, N is added in the graphene oxide obtained into step 1, N '-dimethyl acetamide solution, ultrasonic disperse is uniform, obtains
To dispersion liquid；Dispersion liquid is transferred in thermostat water bath, under conditions of temperature is 60 DEG C and nitrogen protection into dispersion liquid
4 are added in, 4 '-diaminodiphenyl ether I is refluxed 20~28h, then first adds in phenyl silsesquioxane, ultrasound point thereto
Dissipate uniformly after add silane coupling agent, continue stirring to after mixing, add in again 4,4 '-diaminodiphenyl ether II and
12h is stirred at room temperature in pyromellitic dianhydride, obtains a nanometer phenyl silsesquioxane/graphene oxide/polyamic acid solution；
The mass ratio of graphene oxide and 4,4 '-diaminodiphenyl ether I is 2:3；The additive amount of graphene oxide is 4,4 '-diamino two
The 0.1%~0.9% of phenylate II and pyromellitic acid anhydride gross mass；The additive amount of phenyl silsesquioxane is 4,4 '-diamino
The 1%~3% of yl diphenyl ether II and pyromellitic acid anhydride gross mass；The quality and N of the 4,4 '-diaminodiphenyl ether II,
The volume ratio of N '-dimethyl acetamide solution is 1g:12mL；4,4 '-diaminodiphenyl ether II and pyromellitic acid anhydride rub
You are than being 99:100；
3rd, it is 50 that the nanometer phenyl silsesquioxane/graphene oxide/polyamic acid solution obtained step 2, which is transferred to temperature,
DEG C thermostat water bath in heating degradation 30min after, carry out plastic film mulch processing, 300 are then heated to by the way of gradient increased temperature
DEG C carry out hot imidization, be cooled to room temperature, obtain POSS/ODA-GO/PI laminated films.
2. a kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film according to claim 1
Preparation method, it is characterised in that the quality of expanded graphite described in step 1 and the volume ratio of mixed acid solution are 1g:100mL.
3. a kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film according to claim 1
Preparation method, it is characterised in that the mass ratio of expanded graphite described in step 1 and potassium permanganate is 1:6.
4. a kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film according to claim 1
Preparation method, it is characterised in that the feed postition of potassium permanganate described in step 1 is as follows：By 6 throwings of potassium permanganate average mark
Add, per minor tick 10min.
5. a kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film according to claim 1
Preparation method, it is characterised in that the deionized water at the uniform velocity added in the quality and temperature-rise period of expanded graphite described in step 1
Volume ratio is 1g:200mL.
6. a kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film according to claim 1
Preparation method, it is characterised in that silane coupling agent described in step 2 is 3- aminopropyl trimethoxysilanes, often adds 4,4 '-two
1% phenyl silsesquioxane of amino-diphenylethers II and pyromellitic acid anhydride gross mass, 5 drop silane coupling agent of addition.
7. a kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film according to claim 1
Preparation method, it is characterised in that the feed postition of pyromellitic acid anhydride described in step 2 is as follows：By pyromellitic acid anhydride
Average mark adds for 6 times, per minor tick 15min.
8. a kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film according to claim 1
Preparation method, it is characterised in that the additive amount of graphene oxide described in step 2 is 4,4 '-diaminodiphenyl ether II and equal benzene
The 0.5% of tetracarboxylic acid dianhydride gross mass.
9. a kind of phenyl silsesquioxane/graphene oxide/polyimides three-phase composite film according to claim 1
Preparation method, it is characterised in that gradient increased temperature described in step 3 is that temperature is warming up to 80 DEG C from 50 DEG C, and is 80 in temperature
0.5h is kept under conditions of DEG C, then temperature is warming up to 120 DEG C, and keep 0.5h under conditions of being 120 DEG C in temperature by 80 DEG C,
Then temperature is warming up to 150 DEG C by 120 DEG C, 0.5h is kept, then temperature is risen by 150 DEG C under conditions of being 150 DEG C in temperature
Temperature keeps 0.5h, then temperature is warming up to 200 DEG C by 180 DEG C under conditions of being 180 DEG C in temperature, is in temperature to 180 DEG C
0.5h is kept under conditions of 200 DEG C.Temperature is warming up to 250 DEG C by 200 DEG C again, is kept under conditions of being 250 DEG C in temperature
0.5h.Temperature is warming up to 300 DEG C by 250 DEG C again, 0.5h is kept under conditions of being 300 DEG C in temperature.
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