CN105037766A - SiO2Preparation method of hollow sphere/graphene oxide/polyimide composite film - Google Patents
SiO2Preparation method of hollow sphere/graphene oxide/polyimide composite film Download PDFInfo
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Abstract
The invention relates to a SiO2 Hollow ball/Graphene oxide/A method for preparing a polyimide composite film. The base material of the prior copper clad laminate adopts a copper clad polyimide film PI, PI The electric insulation, high temperature resistance, fire resistance that have, along with electronic information product is to high-speed development of high frequency, integrated circuit signal resistance capacity delay, crosstalk and energy consumption problem also are highlighted gradually, and the signal transmission characteristic of printing board receives the influence of printing board substrate dielectric constant and dielectric loss very big, in order to satisfy the high-speed of signal transmission, improves the electronic circuit function, need urgently to develop novel low dielectric constant material and solve above-mentioned problem. The invention comprises the following steps: preparation of the core by template method - Shell "structure of microspheres in 650 Sintering at a temperature of 3h To prepare the nano silicon dioxide hollowHeart ball and by improvement Hummers Preparing the graphene oxide nanosheet by using a method. The invention is used for SiO2 Hollow ball/Graphene oxide/A method for preparing a polyimide composite film.
Description
technical field:
the present invention relates to insulating material technical field, be specifically related to a kind of SiO
2
the method for making of hollow ball/graphene oxide/polyimide composite film.
background technology:
the base material of current copper coated foil plate mainly adopts and covers Copper Foil Kapton, polyimide has excellent electrical insulation capability, mechanical property, resistance to elevated temperatures, flame retardant properties and weather-resistant property etc., but along with electronics and IT products develop to high-frequency high-speedization, in unicircuit, signal appearance delays late, the problem such as crosstalk and energy consumption also highlights day by day, and the signal transmission characteristics of printed board is very large by the impact of pcb substrate specific inductivity and dielectric loss, in order to meet the high speed of signal transmission, the function of further raising electronic circuit, need development of new advanced low-k materials badly to solve the problem, therefore preparation has low-k, the Nano-meter SiO_2 of high heat resistance and good over-all properties
2
hollow ball/graphene oxide/composite polyimide material has very important significance.
along with large-scale integrated circuit size narrows down to the complicated degree of submicron order and circuit and the raising of signal transmission speed, wire density in chip constantly increases, conductor width and spacing constantly reduce, the ghost effect that resistance in interconnected and electric capacity produce is more and more obvious, in order to reduce nanoscale microelectronic device capacitance-resistance time delay caused by signal delay, crosstalks etc., then need the polyimide material of more low-k.Therefore, researchist gets down to and carries out study on the modification to polyimide, wherein be proved and compare one of effective means and in polyimide matrix, introduce inorganic nano-particle exactly, inorganic nano-particle specific surface area is large, functional group contained by surface is more, new chemical bonding structure can be formed with polyimide matrix material, this structure is conducive to giving the better dielectric properties of polyimide and mechanical property etc., as the inorganic nano-particle of polyimide modified dose, what current research was more has silicon-dioxide, the nanoparticles such as aluminum oxide, the polyimide/silicon dioxide nano composite material prepared by sol-gel method, when dioxide-containing silica within the specific limits time, mechanical property and the thermal characteristics of hybrid material significantly improve, hydrothermal method is adopted to prepare nano aluminium oxide dispersion liquid, and then the polyimide/aluminium oxide nano matrix material of preparation, its disruptive strength and corona resistance are obtained for obvious lifting, above-mentioned each side only have studied the research of inorganic nano-particle to the one-sided performance of polyimide, for polyimide three-phase composite material electrical property, the research of the over-all propertieies such as thermal characteristics and power performance is rare to be related to.
summary of the invention:
the object of this invention is to provide a kind of SiO
2
the method for making of hollow ball/graphene oxide/polyimide composite film.
above-mentioned object is realized by following technical scheme:
a kind of SiO
2
the method for making of hollow ball/graphene oxide/polyimide composite film, the method comprises the steps: to adopt template synthesis " core-shell structure copolymer " structure microspheres, 3h is sintered under the condition of 650 DEG C, obtained nano-silicon dioxide hollow sphere, and the Hummers legal system passing through to improve is for stannic oxide/graphene nano sheet;
(1) under room temperature, 0.60g polyacrylic acid and 9mL ammoniacal liquor is added in 250mL there-necked flask, concussion mixes, add rapidly 180mL dehydrated alcohol subsequently, be placed in ultrasonic instrument and stir, divide and in reaction system, add 4.5mL tetraethoxy 6 times, the emulsion of white is obtained after reaction terminates, drying, grinding, 650 DEG C of calcinings, obtain white nano-silicon dioxide hollow sphere;
(2) in there-necked flask, add the 75mL vitriol oil and 25mL concentrated nitric acid mixing solutions, then 2g expanded graphite is added, divide and slowly add 12g potassium permanganate six times, react 1 hour, whole process is all carry out under ice water bath environment, there-necked flask is moved in 35 DEG C of thermostat water baths and continue reaction 2 hours, add appropriate deionized water several times in reaction process and water-bath risen to 98 DEG C of reactions 1 hour, now solution becomes brown, after reaction terminates, add the superoxol that appropriate concentration is 30%, now solution becomes glassy yellow, add the dilution of a large amount of deionized water, filter reactant, remove unreacted potassium permanganate in mixture, by repeatedly centrifugal for the liquid obtained, until pH value is 7, the mixture of gained is dried and grinds, obtain graphite oxide powder, the graphite oxide powder prepared is added in deionized water, ultrasonic vibration 3 hours post-dryings, obtain stannic oxide/graphene nano sheet,
(3) get inorganic content needed for composite property requirement, take stannic oxide/graphene nano sheet, the N of desired number, N '-dimethyl ethanamide joins in there-necked flask; sonic oscillation, mechanical stirring is disperseed, and adds appropriate 4; 4 '-diaminodiphenyl oxide, under nitrogen protection condition, 60 DEG C; backflow 12h; add nano-silicon dioxide hollow sphere, ultrasonic agitation 1h, then; 4 are added, 4 after 60 DEG C of return stirring 12h
'
-diaminodiphenyl oxide, divided by appropriate pyromellitic acid anhydride and join in the middle of system 6 times, when both ratios reach equivalent, system viscosity sharply rises, there is rod climbing phenomenon, continue to stir 24h under obtained nano-silicon dioxide hollow sphere/graphene oxide/polyamic acid solution room temperature;
(4) by obtained nano-silicon dioxide hollow sphere-graphene oxide/polyamic acid solution, through automatic film paving machine film forming on glass, be placed in baking oven, gradient increased temperature imidization, the control of hot imidization process temperature is: 80 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 250 DEG C, 300 DEG C each 30min;
(5) treat naturally cooling, the sheet glass with nano-silicon dioxide hollow sphere-graphene oxide/polyimide composite film is put into deionized water and carries out demoulding, put into loft drier after drying and carry out processed.
described SiO
2
the method for making of hollow ball/graphene oxide/polyimide composite film, described nano-silicon dioxide hollow sphere is loaded in graphene oxide, graphene oxide is through 4, the process of 4 '-diaminodiphenyl oxide, the two passes through chemical bond linkage, the interlamellar spacing of graphene oxide microplate is increased further, being conducive to described hollow silica ball enters between graphene oxide lamella, to peel off further, not only make to be conducive to graphene oxide dispersion, more contribute to three phase materials being uniformly distributed in recombination process, this process need under protective atmosphere, nitrogen protection and argon shield.
described SiO
2
the method for making of hollow ball/graphene oxide/polyimide composite film, described nano-silicon dioxide hollow sphere/graphene oxide/polyimide three components be compounded with help reduce polyimide specific inductivity and improve its mechanical property.
described SiO
2
the method for making of hollow ball/graphene oxide/polyimide composite film, by regulating the ratio of hollow silica ball and graphene oxide to change composite polyimide material performance in described nano-silicon dioxide hollow sphere/graphene oxide/polyimide three components matrix material.
beneficial effect:
1. the present invention is mainly used in high speed integrated circuit flexible clad-copper laminate base material, adopt template synthesis nano silica microsphere, high temperature sintering 3h under the condition of 650 DEG C, obtained nano-silicon dioxide hollow sphere, and Hummer ' the s legal system passing through to improve is for stannic oxide/graphene nano sheet, known by transmission electron microscope characterization result, nano-silicon dioxide hollow sphere good dispersion, there is no obvious agglomeration, and smooth surface, particle diameter are between 50-70nm
2. the present invention is thinner, homogeneous by the graphene oxide lamella that the Hummers legal system of improvement is standby, by Nano-meter SiO_2
2
hollow ball loads to matrix material stannic oxide/graphene nano sheet being filled in polyimide matrix and preparing a kind of dielectric properties, thermal characteristics, satisfactory mechanical property, can be widely used in high speed integrated circuit flexible clad-copper laminate base material.
the invention has the advantages that the nano-silicon dioxide hollow sphere uniform particle sizes by template synthesis, smooth surface, degree of scatter is high, thinner, homogeneous by the standby graphene oxide lamella of Hummers legal system improved, itself and SiO
2
in polyimide matrix, good dispersion is shown after hollow ball load, and Nano-meter SiO_2
2
hollow ball/graphene oxide/composite polyimide material has the features such as excellent dielectric properties, thermal stability and mechanical property.
nano-hollow ball of the present invention is as a kind of new nanostructure, and an one obvious feature is exactly have very large internal space and the shell of thickness within the scope of nanoscale, Nano-meter SiO_2
2
the hollow structure (the specific inductivity k ≈ 1 of air) of hollow ball uniqueness makes its specific inductivity greatly reduce, and nano-silicon dioxide hollow sphere also to have rate of moisture absorption be zero, mechanical property is excellent, many excellent specific properties such as good thermal stability, the matrix material of itself and polyimide can to meet in high speed integrated circuit new technology for the requirement of baseplate material.
graphene oxide of the present invention is a kind of new carbon of excellent performance, as a kind of important derivatives of Graphene, graphene oxide is substantially identical with the structure of Graphene, the basal plane that the two-dimensional space just formed at one deck carbon atom infinitely extends is connected with a large amount of oxy radical, containing hydroxyl and epoxy group(ing) in its plane, and carbonyl and carboxyl is contained at its lamella edge, these functional groups impart the character of some uniquenesses of graphene oxide, easy water suction and stable micellar solution can be formed in water solution system, because graphene oxide specific surface area is large, the intensity and the absorption property that add its matrix material rear are enhanced, improving the calorifics of material, electricity, the over-all properties aspects such as mechanics play very important effect.
the sphere aggregates that the present invention is formed with polyacrylic acid in alcohol solvent is for template, tetraethoxy is as silicon source, nano-silicon dioxide hollow sphere is prepared through sintering, and with silane coupling agent by nano-silicon dioxide hollow sphere with adopt standby graphene oxide-loaded of Hummer ' the s legal system improved, by modified Nano-meter SiO_2
2
hollow ball/graphene oxide powder and polyamic acid compound, prepare the Nano-meter SiO_2 with good dielectric properties, thermal characteristics through Overheating Treatment
2
hollow ball/graphene oxide/composite polyimide material.
accompanying drawing illustrates:
accompanying drawing 1 is the graphene oxide powder X ray diffracting spectrum taking expanded graphite as raw material and prepare of the present invention.
accompanying drawing 2 be method of the present invention obtain 4, the X ray diffracting spectrum of 4 '-diaminodiphenyl oxide-graphene oxide.
accompanying drawing 3 is the X ray diffracting spectrums of the nano-silicon dioxide hollow sphere that method of the present invention obtains.
accompanying drawing 4 is the patterns (transmission electron microscope picture) of the graphene oxide that method of the present invention obtains.
accompanying drawing 5 be method of the present invention obtain 4, the pattern (transmission electron microscope picture) of 4 '-diaminodiphenyl oxide-graphene oxide.
accompanying drawing 6 is the patterns (transmission electron microscope picture) of the nano-silicon dioxide hollow sphere that method of the present invention obtains.
accompanying drawing 7 is patterns (transmission electron microscope picture) of the nanometer SHS-GO powder of the nano-silicon dioxide hollow sphere load graphene oxide that method of the present invention obtains.
accompanying drawing 8 is section looks scanning (scanning electron microscope (SEM) photograph) of nano-silicon dioxide hollow sphere-graphene oxide/composite polyimide material that method of the present invention obtains.
embodiment:
embodiment 1:
a kind of method for making of SiO2 hollow ball/graphene oxide/polyimide composite film, the method comprises the steps: to adopt template synthesis " core-shell structure copolymer " structure microspheres, 3h is sintered under the condition of 650 DEG C, obtained nano-silicon dioxide hollow sphere, and the Hummers legal system passing through to improve is for stannic oxide/graphene nano sheet;
(1) under room temperature, 0.60g polyacrylic acid and 9mL ammoniacal liquor is added in 250mL there-necked flask, concussion mixes, add rapidly 180mL dehydrated alcohol subsequently, be placed in ultrasonic instrument and stir, divide and in reaction system, add 4.5mL tetraethoxy 6 times, the emulsion of white is obtained after reaction terminates, drying, grinding, 650 DEG C of calcinings, obtain white nano-silicon dioxide hollow sphere;
(2) in there-necked flask, add the 75mL vitriol oil and 25mL concentrated nitric acid mixing solutions, then 2g expanded graphite is added, divide and slowly add 12g potassium permanganate six times, react 1 hour, whole process is all carry out under ice water bath environment, there-necked flask is moved in 35 DEG C of thermostat water baths and continue reaction 2 hours, add appropriate deionized water several times in reaction process and water-bath risen to 98 DEG C of reactions 1 hour, now solution becomes brown, after reaction terminates, add the superoxol that appropriate concentration is 30%, now solution becomes glassy yellow, add the dilution of a large amount of deionized water, filter reactant, remove unreacted potassium permanganate in mixture, by repeatedly centrifugal for the liquid obtained, until pH value is 7, the mixture of gained is dried and grinds, obtain graphite oxide powder, the graphite oxide powder prepared is added in deionized water, ultrasonic vibration 3 hours post-dryings, obtain stannic oxide/graphene nano sheet,
(3) get inorganic content needed for composite property requirement, take stannic oxide/graphene nano sheet, the N of desired number, N '-dimethyl ethanamide joins in there-necked flask; sonic oscillation, mechanical stirring is disperseed, and adds appropriate 4; 4 '-diaminodiphenyl oxide, under nitrogen protection condition, 60 DEG C; backflow 12h; add nano-silicon dioxide hollow sphere, ultrasonic agitation 1h, then; 4 are added, 4 after 60 DEG C of return stirring 12h
'
-diaminodiphenyl oxide, divided by appropriate pyromellitic acid anhydride and join in the middle of system 6 times, when both ratios reach equivalent, system viscosity sharply rises, there is rod climbing phenomenon, continue to stir 24h under obtained nano-silicon dioxide hollow sphere/graphene oxide/polyamic acid solution room temperature;
(4) by obtained nano-silicon dioxide hollow sphere-graphene oxide/polyamic acid solution, through automatic film paving machine film forming on glass, be placed in baking oven, gradient increased temperature imidization, the control of hot imidization process temperature is: 80 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 250 DEG C, 300 DEG C each 30min;
(5) treat naturally cooling, the sheet glass with nano-silicon dioxide hollow sphere-graphene oxide/polyimide composite film is put into deionized water and carries out demoulding, put into loft drier after drying and carry out processed.
embodiment 2:
the method for making of the SiO2 hollow ball/graphene oxide/polyimide composite film described in embodiment 1, described nano-silicon dioxide hollow sphere is loaded in graphene oxide, graphene oxide is through 4, the process of 4 '-diaminodiphenyl oxide, the two passes through chemical bond linkage, the interlamellar spacing of graphene oxide microplate is increased further, being conducive to described hollow silica ball enters between graphene oxide lamella, to peel off further, not only make to be conducive to graphene oxide dispersion, more contribute to three phase materials being uniformly distributed in recombination process, this process need under protective atmosphere, nitrogen protection and argon shield.
embodiment 3:
the method for making of the SiO2 hollow ball/graphene oxide/polyimide composite film described in embodiment 1, described nano-silicon dioxide hollow sphere/graphene oxide/polyimide three components be compounded with help reduce polyimide specific inductivity and improve its mechanical property.
embodiment 4:
the method for making of the SiO2 hollow ball/graphene oxide/polyimide composite film described in embodiment 1, by regulating the ratio of hollow silica ball and graphene oxide to change composite polyimide material performance in described nano-silicon dioxide hollow sphere/graphene oxide/polyimide three components matrix material.
Claims (4)
1. a SiO
2the method for making of hollow ball/graphene oxide/polyimide composite film, it is characterized in that: the method comprises the steps: to adopt template synthesis " core-shell structure copolymer " structure microspheres, 3h is sintered under the condition of 650 DEG C, obtained nano-silicon dioxide hollow sphere, and the Hummers legal system passing through to improve is for stannic oxide/graphene nano sheet;
(1) under room temperature, 0.60g polyacrylic acid and 9mL ammoniacal liquor is added in 250mL there-necked flask, concussion mixes, add rapidly 180mL dehydrated alcohol subsequently, be placed in ultrasonic instrument and stir, divide and in reaction system, add 4.5mL tetraethoxy 6 times, the emulsion of white is obtained after reaction terminates, drying, grinding, 650 DEG C of calcinings, obtain white nano-silicon dioxide hollow sphere;
(2) in there-necked flask, add the 75mL vitriol oil and 25mL concentrated nitric acid mixing solutions, then 2g expanded graphite is added, divide and slowly add 12g potassium permanganate six times, react 1 hour, whole process is all carry out under ice water bath environment, there-necked flask is moved in 35 DEG C of thermostat water baths and continue reaction 2 hours, add appropriate deionized water several times in reaction process and water-bath risen to 98 DEG C of reactions 1 hour, now solution becomes brown, after reaction terminates, add the superoxol that appropriate concentration is 30%, now solution becomes glassy yellow, add the dilution of a large amount of deionized water, filter reactant, remove unreacted potassium permanganate in mixture, by repeatedly centrifugal for the liquid obtained, until pH value is 7, the mixture of gained is dried and grinds, obtain graphite oxide powder, the graphite oxide powder prepared is added in deionized water, ultrasonic vibration 3 hours post-dryings, obtain stannic oxide/graphene nano sheet,
(3) get inorganic content needed for composite property requirement, take stannic oxide/graphene nano sheet, the N of desired number, N '-dimethyl ethanamide joins in there-necked flask; sonic oscillation, mechanical stirring is disperseed, and adds appropriate 4; 4 '-diaminodiphenyl oxide, under nitrogen protection condition, 60 DEG C; backflow 12h; add nano-silicon dioxide hollow sphere, ultrasonic agitation 1h, then; 4 are added, 4 after 60 DEG C of return stirring 12h
'-diaminodiphenyl oxide, divided by appropriate pyromellitic acid anhydride and join in the middle of system 6 times, when both ratios reach equivalent, system viscosity sharply rises, there is rod climbing phenomenon, continue to stir 24h under obtained nano-silicon dioxide hollow sphere/graphene oxide/polyamic acid solution room temperature;
(4) by obtained nano-silicon dioxide hollow sphere-graphene oxide/polyamic acid solution, through automatic film paving machine film forming on glass, be placed in baking oven, gradient increased temperature imidization, the control of hot imidization process temperature is: 80 DEG C, 120 DEG C, 150 DEG C, 180 DEG C, 200 DEG C, 250 DEG C, 300 DEG C each 30min;
(5) treat naturally cooling, the sheet glass with nano-silicon dioxide hollow sphere-graphene oxide/polyimide composite film is put into deionized water and carries out demoulding, put into loft drier after drying and carry out processed.
2. SiO according to claim 1
2the method for making of hollow ball/graphene oxide/polyimide composite film, it is characterized in that: described nano-silicon dioxide hollow sphere is loaded in graphene oxide, graphene oxide is through 4, the process of 4 '-diaminodiphenyl oxide, the two passes through chemical bond linkage, the interlamellar spacing of graphene oxide microplate is increased further, being conducive to described hollow silica ball enters between graphene oxide lamella, to peel off further, not only make to be conducive to graphene oxide dispersion, more contribute to three phase materials being uniformly distributed in recombination process, this process need under protective atmosphere, nitrogen protection and argon shield.
3. SiO according to claim 1
2the method for making of hollow ball/graphene oxide/polyimide composite film, is characterized in that: described nano-silicon dioxide hollow sphere/graphene oxide/polyimide three components be compounded with help reduce polyimide specific inductivity and improve its mechanical property.
4. SiO according to claim 1
2the method for making of hollow ball/graphene oxide/polyimide composite film, is characterized in that: by regulating the ratio of hollow silica ball and graphene oxide to change composite polyimide material performance in described nano-silicon dioxide hollow sphere/graphene oxide/polyimide three components matrix material.
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| CN114149685B (en) * | 2021-10-28 | 2023-09-05 | 安能(广州)科学技术有限公司 | High-frequency high-speed copper-clad plate containing nano inorganic mullite alumina hollow microbeads |
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