CN103923332A - Method for preparing nano SiO2 hollow ball composite materials based on polyimide base body - Google Patents
Method for preparing nano SiO2 hollow ball composite materials based on polyimide base body Download PDFInfo
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- CN103923332A CN103923332A CN201410200866.7A CN201410200866A CN103923332A CN 103923332 A CN103923332 A CN 103923332A CN 201410200866 A CN201410200866 A CN 201410200866A CN 103923332 A CN103923332 A CN 103923332A
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Abstract
The invention provides a method for preparing nano SiO2 hollow ball composite materials based on a polyimide base body, and relates to preparation of the nano SiO2 hollow ball composite materials. The method mainly solves the problems that in the prior art, a prepared polyimide thin film is high in dielectric constant, and the technical requirement for base materials in the electronic industry can not be met easily. The method comprises the steps of firstly preparing nano SiO2 hollow ball powder, secondly preparing a nano SiO2 hollow ball/polyamide acid glue liquor, thirdly preparing three layers of nano SiO2 hollow ball/polyamide acid thin film, fourthly conducting thermal amination and fifthly conducting demolding to obtain the nano SiO2 hollow ball composite materials based on the polyimide base body. The dielectric constant of the prepared nano SiO2 hollow ball composite materials based on the polyimide base body is lower than 1.9, and the method can be widely applied to flexible copper-clad foil plate base materials of high-speed integrated circuits. The method is used for preparing the nano SiO2 hollow ball composite materials based on the polyimide base body.
Description
Technical field
The present invention relates to nanometer SiO
2the preparation of Hollow Sphere Composites.
Background technology
The base material of flexible copper-clad paper tinsel plate mainly adopts and covers Copper Foil Kapton (PI) at present, PI has excellent electrical insulation capability, mechanical property, high thermal resistance, chemical stability, flame retardant properties and weather-resistant property etc., but along with electronics and IT products are to high-speed high frequencyization development, in the urgent need to being applied to the copper coated foil plate base material with low-k, low dielectric loss, high thermal resistance in this field.Therefore preparation has the nanometer SiO of high heat resistance, dielectric properties and good over-all properties
2hollow ball/PI matrix material, for meeting flexible printed-circuit board, with base material-copper-clad laminate, the development in insulating material field has very important significance.
Polyimide is first synthetic by Bogert and Renshaw as far back as 20 beginnings of the century, and industrial, has obtained application in the sixties in 20th century.Yet, along with large-scale integrated circuit size narrows down to the raising of complicated degree and the signal transmission speed of submicron order and circuit, wire density in chip constantly increases, and conductor width and spacing constantly reduce, and the ghost effect that the resistance in interconnected and electric capacity produce is more and more obvious.In order to reduce the caused signal delay of capacitance-resistance time delay of nanoscale microelectronic device, crosstalk etc., need the more polyimide material of low-k.Therefore, researchist gets down to PI is carried out to study on the modification, is wherein proved one of comparison effective means and in PI, introduces exactly inorganic nano-particle.Inorganic nano-particle specific surface area is large, and surperficial contained functional group is more, can form new chemical bonding structure with polyimide matrix material, and this structure is conducive to give the better dielectric properties of PI and mechanical property etc.
Recently, there are a lot of researchers to get down to research low dielectric coefficient polyimide, comprise the new type polyimide materials such as fluorinated type polyimide and multi-hole type polyimide.Fluorination generally can strengthen the handiness of molecular chain and reduce the second-order transition temperature of polyimide.Therefore, the use temperature upper limit of fluorinated type polyimide has also been lowered.And the PI after fluoridizing and the decline of material surface adhesiveproperties, under high temperature, HF has corrosive nature to microchip, and the dielectric coefficient of fluoridizing PI is difficult to drop to below 2.0.The method of preparing porous polyimide comprises the use of whipping agent and the embedding of hollow ball.In addition, porous polyimide also can be prepared by the decomposition of segmented copolymer unstable component.The specific inductivity of the Silica Nanotube/polyimide composite film of people's researchs such as Yihe Zhang can be reduced to 2.952, what the people such as Qihua Wang studied take silicon dioxide microsphere as template, and the specific inductivity of porous polyimide laminated film prepared by employing hydrofluoric acid etch technology can be reduced to 2.57.In sum, polymide dielectric constant prepared by prior art is high, and specific inductivity, 2.6～3.9, is difficult to meet microelectronic industry for the problem of base material requires.
Summary of the invention
The present invention will solve prior art to exist the Kapton specific inductivity of preparation high, is difficult to meet microelectronic industry for the problem of base material technical requirements, and provides a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites.
The present invention is a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites carries out according to the following steps:
One, preparation nanometer SiO
2hollow spherical powder: 1. at room temperature, the ammoniacal liquor that is 24%～29% with mass percent by polyacrylic acid concussion mixes, and then add dehydrated alcohol in reaction system, and ultrasonic agitation is even, obtains mixed solution; 2. take tetraethoxy, the volume ratio of described tetraethoxy and polyacrylic quality are (7～9) mL:1g; The tetraethoxy average mark taking is joined for 3 times～6 times in the mixed solution that 1. step obtain, and react 1h～2h after adding tetraethoxy at every turn, obtain white emulsion; 3. the white emulsion 2. step being obtained is dried and grinds, and then, under temperature is the condition of 600 ℃～700 ℃, high-temperature calcination 2h～5h, obtains nanometer SiO
2hollow spherical powder;
The volume ratio of the ammoniacal liquor that described polyacrylic quality and mass percent are 24%～29% is 1g:(13～16) mL; Described polyacrylic quality and the volume ratio of dehydrated alcohol are 1g:(250～350) mL;
Two, preparation nanometer SiO
2hollow ball/polyamic acid glue: at ultrasonic power, be under 150w～250w condition, the nanometer SiO that step 1 is obtained
2hollow spherical powder and silane coupling agent join N, in N '-N,N-DIMETHYLACETAMIDE, ultrasonic agitation 12h～24h, in reaction system, add 4 again, 4'-diaminodiphenyl ether, be stirred to 4, 4'-diaminodiphenyl ether dissolves completely, under the condition that is 1000r/min～2000r/min in ice-water bath and stirring velocity, pyromellitic acid anhydride is divided and joined in reaction system for 4 times～8 times, stir 12h～24h, obtain composite glue solution, 30min～60min finally degrades composite glue solution in temperature is the hot water bath of 30 ℃～70 ℃, and filter and remove gas and impurity, obtain nanometer SiO
2hollow ball/polyamic acid glue,
Described nanometer SiO
2the mass ratio of hollow spherical powder and silane coupling agent is 1:(0.03～0.07); Described nanometer SiO
2the quality of hollow spherical powder and N, the volume ratio of N '-N,N-DIMETHYLACETAMIDE is 1g:(30～600) mL; Described nanometer SiO
2the mass ratio of hollow spherical powder and 4,4'-diaminodiphenyl ether is 1:(2～60); Described 4,4'-diaminodiphenyl ether with the amount of substance of pyromellitic acid anhydride than being 1:1;
Three, three layers of nanometer SiO
2the preparation of hollow ball/Polyamic Acid Film: adopt automatic film paving machine to take the nanometer SiO that plastic film mulch speed obtains on glass even tiling one deck step 2 of cleaning under 2mm/s～6mm/s
2hollow ball/polyamic acid glue, is to dry 30min～60min under the condition of 80 ℃～100 ℃ in temperature, obtains surface and is covered with nanometer SiO
2the glass of hollow ball/Polyamic Acid Film; Then the nanometer SiO obtaining with step 2
2hollow ball/polyamic acid glue is electrostatic spinning liquid, adopts electrospinning process on surface, to be covered with nanometer SiO
2the nanometer SiO that the electrostatic spinning last layer step 2 on glass of hollow ball/Polyamic Acid Film obtains
2hollow ball/polyamic acid glue is dried 30min～60min after electrostatic spinning completes under temperature is the condition of 80 ℃～100 ℃, obtains surface and is covered with double-layer nanometer SiO
2the glass of hollow ball/Polyamic Acid Film; Finally adopt automatic film paving machine to take plastic film mulch speed and under 2mm/s～6mm/s, on surface, be covered with double-layer nanometer SiO
2the nanometer SiO that on glass even tiling one deck step 2 of hollow ball/Polyamic Acid Film obtains
2hollow ball/polyamic acid glue, vacuum-drying 30min～60min, obtains surface and is covered with three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film;
Four, hot imidization: the surface that step 3 is obtained is covered with three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film carries out gradient increased temperature imidization, obtains surface and is covered with nanometer SiO
2the glass of hollow ball/polyimide composite film;
Described gradient increased temperature imidization concrete operations are as follows: first surface is covered with to three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film is warming up to 50 ℃～90 ℃ from room temperature, and in temperature, be to keep 0.5h～1h under the condition of 50 ℃～90 ℃, again temperature is warming up to 100 ℃～130 ℃ by 50 ℃～90 ℃, and in temperature, be to keep 0.5h～1h under the condition of 100 ℃～130 ℃, then temperature is warming up to 140 ℃～160 ℃ by 100 ℃～130 ℃, in temperature, be to keep 0.5h～1h under the condition of 140 ℃～160 ℃, again temperature is warming up to 180 ℃～200 ℃ by 140 ℃～160 ℃, in temperature, be to keep 0.5h～1h under the condition of 180 ℃～200 ℃, then temperature is warming up to 210 ℃～240 ℃ by 180 ℃～200 ℃, in temperature, be to keep 0.5h～1h under the condition of 210 ℃～240 ℃, again temperature is warming up to 250 ℃～280 ℃ by 210 ℃～240 ℃, in temperature, be to keep 0.5h～1h under the condition of 250 ℃～280 ℃, finally temperature is warming up to 300 ℃～350 ℃ by 250 ℃～280 ℃, in temperature, be to keep 0.5h～1h under the condition of 300 ℃～350 ℃,
Five, demoulding: the surface that step 4 is obtained is covered with nanometer SiO
2the glass of hollow ball/polyimide composite film naturally cools to room temperature, and is placed in deionized water and carries out demoulding, obtains nanometer SiO
2then hollow ball/polyimide composite film is by nanometer SiO under the condition of 80 ℃～120 ℃ in temperature
2hollow ball/polyimide composite film carries out processed 2h～5h, obtains based on polyimide matrix nanometer SiO
2hollow Sphere Composites.
The invention has the beneficial effects as follows:
The present invention adopts the nanometer SiO of template synthesis
2hollow ball particle diameter is even, smooth surface, and degree of scatter is high; Hollow ball particle diameter is approximately between 50nm～70nm, and internal diameter is between 20nm～30nm, and wall thickness is about 15nm left and right; Nanometer SiO
2hollow ball whole dispersion in polyimide matrix is more even; The matrix material good thermal stability of itself and polyimide; The three-decker polyimide composite film specific inductivity of preparing by method of electrostatic spinning can further reduce, and can be widely used in flexible copper-clad paper tinsel plate substrate.Within the scope of the filling of this patent research, along with nanometer SiO
2hollow ball accounts for final product based on polyimide matrix nanometer SiO
2the increase of the quality percentage composition of Hollow Sphere Composites, the specific inductivity of laminated film prepared by method of electrostatic spinning first reduces rear rising, as nanometer SiO
2hollow ball accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is low to moderate 1.9 left and right while being 10%.In sum, nanometer SiO
2hollow ball/composite polyimide material can be widely used in high speed integrated circuit flexible copper-clad paper tinsel plate substrate.
The present invention is for a kind of based on polyimide matrix nanometer SiO
2the preparation of Hollow Sphere Composites.
Accompanying drawing explanation
Fig. 1 is the nanometer SiO that embodiment mono-step 1 obtains
2hollow spherical powder transmission electron microscope picture;
Fig. 2 is the nanometer SiO that embodiment mono-step 1 obtains
2hollow spherical powder scanning electron microscope (SEM) photograph;
Fig. 3 is the nanometer SiO that embodiment mono-step 2 obtains
2hollow ball/polyamic acid glue is spun into the scanning electron microscope (SEM) photograph after fiber;
Fig. 4 be embodiment mono-preparation based on polyimide matrix nanometer SiO
2hollow Sphere Composites section SEM figure;
Fig. 5 be embodiment tri-preparation based on polyimide matrix nanometer SiO
2hollow Sphere Composites section SEM figure;
Fig. 6 be embodiment five preparation based on polyimide matrix nanometer SiO
2hollow Sphere Composites section SEM figure;
Fig. 7 be embodiment seven preparation based on polyimide matrix nanometer SiO
2hollow Sphere Composites section SEM figure;
Fig. 8 is based on polyimide matrix nanometer SiO
2the dielectric material graphic representation of Hollow Sphere Composites.
Embodiment
Embodiment one: a kind of based on polyimide matrix nanometer SiO described in present embodiment
2the preparation method of Hollow Sphere Composites, specifically carries out according to following steps:
One, preparation nanometer SiO
2hollow spherical powder: 1. at room temperature, the ammoniacal liquor that is 24%～29% with mass percent by polyacrylic acid concussion mixes, and then add dehydrated alcohol in reaction system, and ultrasonic agitation is even, obtains mixed solution; 2. take tetraethoxy, the volume ratio of described tetraethoxy and polyacrylic quality are (7～9) mL:1g; The tetraethoxy average mark taking is joined for 3 times～6 times in the mixed solution that 1. step obtain, and react 1h～2h after adding tetraethoxy at every turn, obtain white emulsion; 3. the white emulsion 2. step being obtained is dried and grinds, and then, under temperature is the condition of 600 ℃～700 ℃, high-temperature calcination 2h～5h, obtains nanometer SiO
2hollow spherical powder;
The volume ratio of the ammoniacal liquor that described polyacrylic quality and mass percent are 24%～29% is 1g:(13～16) mL; Described polyacrylic quality and the volume ratio of dehydrated alcohol are 1g:(250～350) mL;
Two, preparation nanometer SiO
2hollow ball/polyamic acid glue: at ultrasonic power, be under 150w～250w condition, the nanometer SiO that step 1 is obtained
2hollow spherical powder and silane coupling agent join N, in N '-N,N-DIMETHYLACETAMIDE, ultrasonic agitation 12h～24h, in reaction system, add 4 again, 4'-diaminodiphenyl ether, be stirred to 4, 4'-diaminodiphenyl ether dissolves completely, under the condition that is 1000r/min～2000r/min in ice-water bath and stirring velocity, pyromellitic acid anhydride is divided and joined in reaction system for 4 times～8 times, stir 12h～24h, obtain composite glue solution, 30min～60min finally degrades composite glue solution in temperature is the hot water bath of 30 ℃～70 ℃, and filter and remove gas and impurity, obtain nanometer SiO
2hollow ball/polyamic acid glue,
Described nanometer SiO
2the mass ratio of hollow spherical powder and silane coupling agent is 1:(0.03～0.07); Described nanometer SiO
2the quality of hollow spherical powder and N, the volume ratio of N '-N,N-DIMETHYLACETAMIDE is 1g:(30～600) mL; Described nanometer SiO
2the mass ratio of hollow spherical powder and 4,4'-diaminodiphenyl ether is 1:(2～60); Described 4,4'-diaminodiphenyl ether with the amount of substance of pyromellitic acid anhydride than being 1:1;
Three, three layers of nanometer SiO
2the preparation of hollow ball/Polyamic Acid Film: adopt automatic film paving machine to take the nanometer SiO that plastic film mulch speed obtains on glass even tiling one deck step 2 of cleaning under 2mm/s～6mm/s
2hollow ball/polyamic acid glue, is to dry 30min～60min under the condition of 80 ℃～100 ℃ in temperature, obtains surface and is covered with nanometer SiO
2the glass of hollow ball/Polyamic Acid Film; Then the nanometer SiO obtaining with step 2
2hollow ball/polyamic acid glue is electrostatic spinning liquid, adopts electrospinning process on surface, to be covered with nanometer SiO
2the nanometer SiO that the electrostatic spinning last layer step 2 on glass of hollow ball/Polyamic Acid Film obtains
2hollow ball/polyamic acid glue is dried 30min～60min after electrostatic spinning completes under temperature is the condition of 80 ℃～100 ℃, obtains surface and is covered with double-layer nanometer SiO
2the glass of hollow ball/Polyamic Acid Film; Finally adopt automatic film paving machine to take plastic film mulch speed and under 2mm/s～6mm/s, on surface, be covered with double-layer nanometer SiO
2the nanometer SiO that on glass even tiling one deck step 2 of hollow ball/Polyamic Acid Film obtains
2hollow ball/polyamic acid glue, vacuum-drying 30min～60min, obtains surface and is covered with three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film;
Four, hot imidization: the surface that step 3 is obtained is covered with three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film carries out gradient increased temperature imidization, obtains surface and is covered with nanometer SiO
2the glass of hollow ball/polyimide composite film;
Described gradient increased temperature imidization concrete operations are as follows: first surface is covered with to three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film is warming up to 50 ℃～90 ℃ from room temperature, and in temperature, be to keep 0.5h～1h under the condition of 50 ℃～90 ℃, again temperature is warming up to 100 ℃～130 ℃ by 50 ℃～90 ℃, and in temperature, be to keep 0.5h～1h under the condition of 100 ℃～130 ℃, then temperature is warming up to 140 ℃～160 ℃ by 100 ℃～130 ℃, in temperature, be to keep 0.5h～1h under the condition of 140 ℃～160 ℃, again temperature is warming up to 180 ℃～200 ℃ by 140 ℃～160 ℃, in temperature, be to keep 0.5h～1h under the condition of 180 ℃～200 ℃, then temperature is warming up to 210 ℃～240 ℃ by 180 ℃～200 ℃, in temperature, be to keep 0.5h～1h under the condition of 210 ℃～240 ℃, again temperature is warming up to 250 ℃～280 ℃ by 210 ℃～240 ℃, in temperature, be to keep 0.5h～1h under the condition of 250 ℃～280 ℃, finally temperature is warming up to 300 ℃～350 ℃ by 250 ℃～280 ℃, in temperature, be to keep 0.5h～1h under the condition of 300 ℃～350 ℃,
Five, demoulding: the surface that step 4 is obtained is covered with nanometer SiO
2the glass of hollow ball/polyimide composite film naturally cools to room temperature, and is placed in deionized water and carries out demoulding, obtains nanometer SiO
2then hollow ball/polyimide composite film is by nanometer SiO under the condition of 80 ℃～120 ℃ in temperature
2hollow ball/polyimide composite film carries out processed 2h～5h, obtains based on polyimide matrix nanometer SiO
2hollow Sphere Composites.
3. step 1 makes after white emulsion, also can adopt the method for redistilled water centrifuge washing to prepare nanometer SiO
2hollow spherical powder.
Three layers of nanometer SiO that present embodiment step 3 obtains
2the nanometer SiO that in the glass of hollow ball/Polyamic Acid Film, the first layer obtains through automatic film paving machine
2the thickness of hollow ball/Polyamic Acid Film is 27um～33um; The nanometer SiO that the second layer obtains through electrostatic spinning
2the thickness of hollow ball/Polyamic Acid Film is 17um～23um; The 3rd layer of nanometer SiO obtaining through automatic film paving machine
2the thickness of hollow ball/Polyamic Acid Film is 27um～33um.
White nanometer SiO
2the particle diameter of hollow spherical powder and wall thickness can be controlled by changing consumption, tetraethoxy and the polyacrylic concentration of ammoniacal liquor.
By nanometer SiO
2hollow spherical powder is distributed to N, in N '-N,N-DIMETHYLACETAMIDE, can adopt ultrasonic method, the method that also can adopt ultra-high speed to stir, or two kinds of methods are combined with.
During step 5 plastic film mulch, according to the loading level of inorganic nano-particle and dissolvent solid content, determine the plastic film mulch graduating with cutter degree of required debugging.
The beneficial effect of present embodiment is: present embodiment adopts the nanometer SiO of template synthesis
2hollow ball particle diameter is even, smooth surface, and degree of scatter is high; Hollow ball particle diameter is approximately between 50nm～70nm, and internal diameter is between 20nm～30nm, and wall thickness is about 15nm left and right; Nanometer SiO
2hollow ball whole dispersion in polyimide matrix is more even; The matrix material good thermal stability of itself and polyimide; The three-decker polyimide composite film specific inductivity of preparing by method of electrostatic spinning can further reduce, and can be widely used in flexible copper-clad paper tinsel plate substrate.Within the scope of the filling of this patent research, along with nanometer SiO
2hollow ball accounts for final product based on polyimide matrix nanometer SiO
2the increase of the quality percentage composition of Hollow Sphere Composites, the specific inductivity of laminated film prepared by method of electrostatic spinning first reduces rear rising, as nanometer SiO
2hollow ball accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is low to moderate 1.9 left and right while being 10%.In sum, nanometer SiO
2hollow ball/composite polyimide material can be widely used in high speed integrated circuit flexible copper-clad paper tinsel plate substrate.
The sphere aggregates that the polyacrylic acid of take forms in alcohol solvent is template, and tetraethoxy, as silicon source, is prepared nanometer SiO through sintering
2hollow ball, itself and polyamic acid is compound, and add silane coupling agent to strengthen the consistency between organic-inorganic, through Overheating Treatment, prepare the nanometer SiO with good dielectric properties, thermal characteristics
2hollow ball/PI matrix material.
Nano-hollow ball is as a kind of new nanostructure, and an one obvious feature is exactly to have very large internal space and the shell of thickness within the scope of nanoscale.Nanometer SiO
2the hollow structure of hollow ball uniqueness (the specific inductivity k=1 of air) reduces its specific inductivity greatly, and nanometer SiO
2it is zero that hollow ball also has rate of moisture absorption, and mechanical property is excellent, many excellent specific properties such as good thermal stability, and the matrix material of itself and polyimide can meet in high speed integrated circuit new technology for the requirement of baseplate material.
Embodiment two: present embodiment is different from embodiment one: the volume ratio of the ammoniacal liquor that the polyacrylic quality described in step 1 and mass percent are 25%～28% is 1g:(14～15) mL.Other is identical with embodiment one.
Embodiment three: present embodiment is different from one of embodiment one or two: the volume ratio of the polyacrylic quality described in step 1 and dehydrated alcohol is 1g:300mL.Other is identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three: the volume ratio of the tetraethoxy described in step 1 and polyacrylic quality are 7.5mL:1g.Other is identical with embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four: the silane coupling agent described in step 2 is 3-aminopropyl trimethoxysilane.Other is identical with embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five: the nanometer SiO described in step 2
2the mass ratio of hollow spherical powder and silane coupling agent is 1:0.05.Other is identical with embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six: quality and the N of the nanometer SiO2 hollow spherical powder described in step 2, the volume ratio of N '-N,N-DIMETHYLACETAMIDE is 1g:(34～586) mL.Other is identical with embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven: the nanometer SiO described in step 2
2the mass ratio of hollow spherical powder and 4,4'-diaminodiphenyl ether is 1:(3～52).Other is identical with embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight: electrostatic spinning described in step 3 is the DT-200 type electrostatic spinning machine that adopts Dalian Ding Tong Science and Technology Ltd. to produce, in spinning voltage, be 30kv, receiving angle is 90 °, receiving range is 15～20cm, shower nozzle diameter is 1.3mm, syringe fltting speed is 0.0125mm/min, and X-axis sweep velocity is 100mm/min, carries out spinning 2h.Other is identical with embodiment one to eight.
Embodiment ten: present embodiment is different from one of embodiment one to nine: the gradient increased temperature imidization concrete operations described in step 4 are as follows: first surface is covered with to three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film is warming up to 80 ℃ from room temperature, and in temperature, be to keep 30min under the condition of 80 ℃, again temperature is warming up to 120 ℃ by 80 ℃, and in temperature, be to keep 30min under the condition of 120 ℃, then temperature is warming up to 150 ℃ by 120 ℃, in temperature, be to keep 30min under the condition of 150 ℃, again temperature is warming up to 180 ℃ by 150 ℃, in temperature, be to keep 30min under the condition of 180 ℃, then temperature is warming up to 220 ℃ by 180 ℃, in temperature, be to keep 30min under the condition of 220 ℃, then temperature is warming up to 250 ℃ by 220 ℃, in temperature, be to keep 30min under the condition of 250 ℃, finally temperature is warming up to 300 ℃ by 250 ℃, in temperature, be to keep 30min under the condition of 300 ℃.Other is identical with embodiment one to nine.
By following examples, verify beneficial effect of the present invention:
Embodiment mono-: a kind of based on polyimide matrix nanometer SiO described in the present embodiment
2the preparation method of Hollow Sphere Composites, specifically carries out according to following steps:
One, preparation nanometer SiO
2hollow spherical powder: 1. at room temperature, the ammoniacal liquor that is 25%～28% with 9mL mass percent by 0.6g polyacrylic acid concussion mixes, and then add 180mL dehydrated alcohol in reaction system, and ultrasonic agitation is even, obtains mixed solution; 2. in the mixed solution 1. obtaining to step, add 0.9mL tetraethoxy, reaction 1h; 3. repeating step is 2. 5 times, obtains white emulsion; 4. the white emulsion 3. step being obtained is dried and grinds, and in temperature, is then at 650 ℃, and high-temperature calcination 3h, obtains nanometer SiO
2hollow spherical powder;
Two, preparation nanometer SiO
2hollow ball/polyamic acid colloidal sol: at ultrasonic power, be under 200w condition, the nanometer SiO that 0.058g step 1 is obtained
2hollow spherical powder and 3-aminopropyl trimethoxysilane join 34mLN, in N '-N,N-DIMETHYLACETAMIDE, ultrasonic agitation 12h, in reaction system, add 3g4 again, 4'-diaminodiphenyl ether, be stirred to 4,4'-diaminodiphenyl ether dissolves completely, under the condition that is 1000r/min in ice-water bath and stirring velocity, 3.2680g pyromellitic acid anhydride is divided and joined in reaction system for 6 times, stir 12h, obtain composite glue solution, the 30min that finally composite glue solution degraded in temperature is the hot water bath of 50 ℃, and filter and remove gas and impurity, nanometer SiO obtained
2hollow ball/polyamic acid glue;
Described nanometer SiO
2the mass ratio of hollow spherical powder and 3-aminopropyl trimethoxysilane is 1:0.05;
Four, three layers of nanometer SiO
2the preparation of hollow ball/Polyamic Acid Film: adopt automatic film paving machine to take the nanometer SiO that plastic film mulch speed obtains on glass even tiling one deck step 2 of cleaning under 4mm/s
2hollow ball/polyamic acid glue, is to dry 30min under the condition of 80 ℃ in temperature, obtains surface and is covered with nanometer SiO
2the glass of hollow ball/Polyamic Acid Film; Then the nanometer SiO obtaining with step 2
2hollow ball/polyamic acid glue is electrostatic spinning liquid, adopts electrospinning process on surface, to be covered with nanometer SiO
2the nanometer SiO that the electrostatic spinning last layer step 2 on glass of hollow ball/Polyamic Acid Film obtains
2hollow ball/polyamic acid glue is dried 30min after electrostatic spinning completes under temperature is the condition of 80 ℃, obtains surface and is covered with double-layer nanometer SiO
2the glass of hollow ball/Polyamic Acid Film; Finally adopt automatic film paving machine to take plastic film mulch speed and under 4mm/s, on surface, be covered with double-layer nanometer SiO
2the nanometer SiO that on glass even tiling one deck step 2 of hollow ball/Polyamic Acid Film obtains
2hollow ball/polyamic acid glue, vacuum-drying 30min, obtains surface and is covered with three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film;
Four, hot imidization: the surface that step 3 is obtained is covered with three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film carries out gradient increased temperature imidization, obtains surface and is covered with nanometer SiO
2the glass of hollow ball/polyimide composite film;
Described gradient increased temperature imidization concrete operations are as follows: first surface is covered with to three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film is warming up to 80 ℃ from room temperature, and in temperature, be to keep 30min under the condition of 80 ℃, again temperature is warming up to 120 ℃ by 80 ℃, and in temperature, be to keep 30min under the condition of 120 ℃, then temperature is warming up to 150 ℃ by 120 ℃, in temperature, be to keep 30min under the condition of 150 ℃, again temperature is warming up to 180 ℃ by 150 ℃, in temperature, be to keep 30min under the condition of 180 ℃, then temperature is warming up to 220 ℃ by 180 ℃, in temperature, be to keep 30min under the condition of 220 ℃, then temperature is warming up to 250 ℃ by 220 ℃, in temperature, be to keep 30min under the condition of 250 ℃, finally temperature is warming up to 300 ℃ by 250 ℃, in temperature, be to keep 30min under the condition of 300 ℃,
Five, demoulding: the surface that step 4 is obtained is covered with nanometer SiO
2the glass of hollow ball/polymeric amide laminated film naturally cools to room temperature, and is placed in deionized water and carries out demoulding, obtains nanometer SiO
2then hollow ball/polyimide composite film is by nanometer SiO under the condition of 100 ℃ in temperature
2hollow ball/polyimide composite film carries out processed 3h, obtains based on polyimide matrix nanometer SiO
2hollow Sphere Composites.
The present embodiment prepare based on polyimide matrix nanometer SiO
2hollow Sphere Composites as calculated, nanometer SiO
2hollow spherical powder accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is 1%.
Fig. 1 is the nanometer SiO that embodiment mono-step 1 obtains
2hollow spherical powder transmission electron microscope picture; As can be seen from the figure the nanometer SiO that, the present embodiment step 1 obtains
2hollow spherical powder is spherical in shape, and inside is hollow structure.Hollow ball particle diameter is approximately between 50nm～70nm, and internal diameter is between 20nm～30nm, and wall thickness is about 15nm left and right.Hollow ball smooth surface, size distribution are even, and the phenomenon such as do not occur subsiding, break.
Fig. 2 is the nanometer SiO that embodiment mono-step 1 obtains
2hollow spherical powder scanning electron microscope (SEM) photograph; As can be seen from the figure the nanometer SiO that, the present embodiment step 1 obtains
2hollow spherical powder is uniformly dispersed on the whole, there is no obvious agglomeration.
Fig. 3 is the nanometer SiO that embodiment mono-step 2 obtains
2hollow ball/polyamic acid glue is spun into the scanning electron microscope (SEM) photograph after fiber; Nano thread line profile is clear as we can see from the figure, and pattern is more even, good dispersion, and also the situation of node fracture occurs less, satisfactory for result.
Fig. 4 be embodiment mono-preparation based on polyimide matrix nanometer SiO
2hollow Sphere Composites section SEM figure; As can be observed from Figure, in polyimide matrix, contain a small amount of nanometer SiO
2hollow ball, nanometer SiO
2hollow ball particle diameter is less, becomes point-like to be evenly distributed in polyimide matrix, nanometer SiO
2between hollow ball and polyimide matrix, be bonded to each other closely.
Embodiment bis-: the present embodiment is different from embodiment mono-: in step 2 by 0.1775g nanometer SiO
2hollow spherical powder and 3-aminopropyl trimethoxysilane join 34mLN, in N '-N,N-DIMETHYLACETAMIDE, and described nanometer SiO
2the mass ratio of hollow spherical powder and 3-aminopropyl trimethoxysilane is 1:0.05.Other is identical with embodiment one.
The present embodiment prepare based on polyimide matrix nanometer SiO
2hollow Sphere Composites as calculated, nanometer SiO
2hollow spherical powder accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is 3%.
Embodiment tri-: the present embodiment is different from embodiment mono-: in step 2 by 0.3021g nanometer SiO
2hollow spherical powder and 3-aminopropyl trimethoxysilane join 34mLN, in N '-N,N-DIMETHYLACETAMIDE, and described nanometer SiO
2the mass ratio of hollow spherical powder and 3-aminopropyl trimethoxysilane is 1:0.05.Other is identical with embodiment one.
The present embodiment prepare based on polyimide matrix nanometer SiO
2hollow Sphere Composites as calculated, nanometer SiO
2hollow spherical powder accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is 5%.
Fig. 5 be embodiment tri-preparation based on polyimide matrix nanometer SiO
2hollow Sphere Composites section SEM figure; Compare with Fig. 4, can find out the nanometer SiO in polyimide matrix
2hollow spherulite quantum count showed increased, and be uniformly dispersed, nanometer SiO
2between hollow ball and polyimide matrix, closely combine.
Embodiment tetra-: the present embodiment is different from embodiment mono-: in step 2 by 0.4320g nanometer SiO
2hollow spherical powder and 3-aminopropyl trimethoxysilane join 34mLN, in N '-N,N-DIMETHYLACETAMIDE, and described nanometer SiO
2the mass ratio of hollow spherical powder and 3-aminopropyl trimethoxysilane is 1:0.05.Other is identical with embodiment one.
The present embodiment prepare based on polyimide matrix nanometer SiO
2hollow Sphere Composites as calculated, nanometer SiO
2hollow spherical powder accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is 7%.
Embodiment five: the present embodiment is different from embodiment mono-: in step 2 by 0.6378g nanometer SiO
2hollow spherical powder and 3-aminopropyl trimethoxysilane join 34mLN, in N '-N,N-DIMETHYLACETAMIDE, and described nanometer SiO
2the mass ratio of hollow spherical powder and 3-aminopropyl trimethoxysilane is 1:0.05.Other is identical with embodiment one.
The present embodiment prepare based on polyimide matrix nanometer SiO
2hollow Sphere Composites as calculated, nanometer SiO
2hollow spherical powder accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is 10%.
Fig. 6 be embodiment five preparation based on polyimide matrix nanometer SiO
2hollow Sphere Composites section SEM figure; As seen from the figure, the nanometer SiO in polyimide matrix
2the more crypto set that hollow ball particle distributes, that still disperses on the whole is still more even, does not have agglomerating particles to occur.
Embodiment six: the present embodiment is different from embodiment mono-: in step 2 by 0.8577g nanometer SiO
2hollow spherical powder and 3-aminopropyl trimethoxysilane join 34mLN, in N '-N,N-DIMETHYLACETAMIDE, and described nanometer SiO
2the mass ratio of hollow spherical powder and 3-aminopropyl trimethoxysilane is 1:0.05.Other is identical with embodiment one.
The present embodiment prepare based on polyimide matrix nanometer SiO
2hollow Sphere Composites as calculated, nanometer SiO
2hollow spherical powder accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is 13%.
Embodiment seven: the present embodiment is different from embodiment mono-: in step 2 by 1.0129g nanometer SiO
2hollow spherical powder and 3-aminopropyl trimethoxysilane join 34mLN, in N '-N,N-DIMETHYLACETAMIDE, and described nanometer SiO
2the mass ratio of hollow spherical powder and 3-aminopropyl trimethoxysilane is 1:0.05.Other is identical with embodiment one.
The present embodiment prepare based on polyimide matrix nanometer SiO
2hollow Sphere Composites as calculated, nanometer SiO
2hollow spherical powder accounts for final product based on polyimide matrix nanometer SiO
2the quality percentage composition of Hollow Sphere Composites is 15%.
Fig. 7 be embodiment seven preparation based on polyimide matrix nanometer SiO
2hollow Sphere Composites section SEM figure; By the obvious low nanometer SiO that observes of figure
2hollow ball spacing has to each other reduced, and it is very tight that the arrangement in polyimide matrix becomes, and the section of matrix material is uneven.And nanometer SiO
2there is a large amount of agglomerations in hollow ball, destroyed the continuity of polyimide matrix in polyimide matrix.
Embodiment eight: the contrast experiment of embodiment mono-to embodiment seven, the present embodiment is different from embodiment mono-: in step 2 by 0g nanometer SiO
2hollow spherical powder and 0g silane coupling agent join 34mLN, in N '-N,N-DIMETHYLACETAMIDE.Other is identical with embodiment one.
The present embodiment does not add nanometer SiO
2hollow spherical powder, therefore, based on polyimide matrix nanometer SiO
2hollow Sphere Composites is containing nanometer SiO
2the quality percentage composition of hollow spherical powder is 0%.
Fig. 8 is based on polyimide matrix nanometer SiO
2the dielectric material graphic representation of Hollow Sphere Composites; As seen from the figure, under same test frequency, along with nanometer SiO
2hollow ball accounts for final product based on polyimide matrix nanometer SiO
2the increase of the quality percentage composition of Hollow Sphere Composites, laminated film specific inductivity first reduces rear rising.As nanometer SiO
2hollow ball accounts for final product based on polyimide matrix nanometer SiO
2when the quality percentage composition of Hollow Sphere Composites is 10%, specific inductivity is low to moderate 1.9, can prove thus prepared by the present invention based on polyimide matrix nanometer SiO
2hollow Sphere Composites specific inductivity is very low, in high speed integrated circuit flexible copper-clad paper tinsel plate substrate.
By thermal weight loss, test, record based on polyimide matrix nanometer SiO
2the initial heat decomposition temperature of Hollow Sphere Composites is as shown in table 1, as shown in Table 1, and based on polyimide matrix nanometer SiO
2the heat decomposition temperature of Hollow Sphere Composites is more than 590 ℃, and with the heat decomposition temperature comparison of pure polyimide, thermal stability is more or less the same, the do not have a significant effect temperature classification of polyimide of the introducing that inorganic phase is described.Can prove thus prepared by the inventive example based on polyimide matrix nanometer SiO
2the thermotolerance of Hollow Sphere Composites is good, in high speed integrated circuit flexible copper-clad paper tinsel plate substrate.
Table 1: based on polyimide matrix nanometer SiO
2the initial heat decomposition temperature of Hollow Sphere Composites
Claims (10)
1. one kind based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, is characterized in that based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites carries out according to the following steps:
One, preparation nanometer SiO
2hollow spherical powder: 1. at room temperature, the ammoniacal liquor that is 24%～29% with mass percent by polyacrylic acid concussion mixes, and then add dehydrated alcohol in reaction system, and ultrasonic agitation is even, obtains mixed solution; 2. take tetraethoxy, the volume ratio of described tetraethoxy and polyacrylic quality are (7～9) mL:1g; The tetraethoxy average mark taking is joined for 3 times～6 times in the mixed solution that 1. step obtain, and react 1h～2h after adding tetraethoxy at every turn, obtain white emulsion; 3. the white emulsion 2. step being obtained is dried and grinds, and then, under temperature is the condition of 600 ℃～700 ℃, high-temperature calcination 2h～5h, obtains nanometer SiO
2hollow spherical powder;
The volume ratio of the ammoniacal liquor that described polyacrylic quality and mass percent are 24%～29% is 1g:(13～16) mL; Described polyacrylic quality and the volume ratio of dehydrated alcohol are 1g:(250～350) mL;
Two, preparation nanometer SiO
2hollow ball/polyamic acid glue: at ultrasonic power, be under 150w～250w condition, the nanometer SiO that step 1 is obtained
2hollow spherical powder and silane coupling agent join N, in N '-N,N-DIMETHYLACETAMIDE, ultrasonic agitation 12h～24h, in reaction system, add 4 again, 4'-diaminodiphenyl ether, be stirred to 4, 4'-diaminodiphenyl ether dissolves completely, under the condition that is 1000r/min～2000r/min in ice-water bath and stirring velocity, pyromellitic acid anhydride is divided and joined in reaction system for 4 times～8 times, stir 12h～24h, obtain composite glue solution, 30min～60min finally degrades composite glue solution in temperature is the hot water bath of 30 ℃～70 ℃, and filter and remove gas and impurity, obtain nanometer SiO
2hollow ball/polyamic acid glue,
Described nanometer SiO2 hollow spherical powder and the mass ratio of silane coupling agent are 1:(0.03～0.07); Described nanometer SiO
2the quality of hollow spherical powder and N, the volume ratio of N '-N,N-DIMETHYLACETAMIDE is 1g:(30～600) mL; Described nanometer SiO
2the mass ratio of hollow spherical powder and 4,4'-diaminodiphenyl ether is 1:(2～60); Described 4,4'-diaminodiphenyl ether with the amount of substance of pyromellitic acid anhydride than being 1:1;
Three, three layers of nanometer SiO
2the preparation of hollow ball/Polyamic Acid Film: adopt automatic film paving machine to take the nanometer SiO that plastic film mulch speed obtains on glass even tiling one deck step 2 of cleaning under 2mm/s～6mm/s
2hollow ball/polyamic acid glue, is to dry 30min～60min under the condition of 80 ℃～100 ℃ in temperature, obtains surface and is covered with nanometer SiO
2the glass of hollow ball/Polyamic Acid Film; Then the nanometer SiO obtaining with step 2
2hollow ball/polyamic acid glue is electrostatic spinning liquid, adopts electrospinning process on surface, to be covered with nanometer SiO
2the nanometer SiO that the electrostatic spinning last layer step 2 on glass of hollow ball/Polyamic Acid Film obtains
2hollow ball/polyamic acid glue is dried 30min～60min after electrostatic spinning completes under temperature is the condition of 80 ℃～100 ℃, obtains surface and is covered with double-layer nanometer SiO
2the glass of hollow ball/Polyamic Acid Film; Finally adopt automatic film paving machine to take plastic film mulch speed and under 2mm/s～6mm/s, on surface, be covered with double-layer nanometer SiO
2the nanometer SiO that on glass even tiling one deck step 2 of hollow ball/Polyamic Acid Film obtains
2hollow ball/polyamic acid glue, vacuum-drying 30min～60min, obtains surface and is covered with three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film;
Four, hot imidization: the surface that step 3 is obtained is covered with three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film carries out gradient increased temperature imidization, obtains surface and is covered with nanometer SiO
2the glass of hollow ball/polyimide composite film;
Described gradient increased temperature imidization concrete operations are as follows: first surface is covered with to three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film is warming up to 50 ℃～90 ℃ from room temperature, and in temperature, be to keep 0.5h～1h under the condition of 50 ℃～90 ℃, again temperature is warming up to 100 ℃～130 ℃ by 50 ℃～90 ℃, and in temperature, be to keep 0.5h～1h under the condition of 100 ℃～130 ℃, then temperature is warming up to 140 ℃～160 ℃ by 100 ℃～130 ℃, in temperature, be to keep 0.5h～1h under the condition of 140 ℃～160 ℃, again temperature is warming up to 180 ℃～200 ℃ by 140 ℃～160 ℃, in temperature, be to keep 0.5h～1h under the condition of 180 ℃～200 ℃, then temperature is warming up to 210 ℃～240 ℃ by 180 ℃～200 ℃, in temperature, be to keep 0.5h～1h under the condition of 210 ℃～240 ℃, again temperature is warming up to 250 ℃～280 ℃ by 210 ℃～240 ℃, in temperature, be to keep 0.5h～1h under the condition of 250 ℃～280 ℃, finally temperature is warming up to 300 ℃～350 ℃ by 250 ℃～280 ℃, in temperature, be to keep 0.5h～1h under the condition of 300 ℃～350 ℃,
Five, demoulding: the surface that step 4 is obtained is covered with nanometer SiO
2the glass of hollow ball/polyimide composite film naturally cools to room temperature, and is placed in deionized water and carries out demoulding, obtains nanometer SiO
2then hollow ball/polyimide composite film is by nanometer SiO under the condition of 80 ℃～120 ℃ in temperature
2hollow ball/polyimide composite film carries out processed 2h～5h, obtains based on polyimide matrix nanometer SiO
2hollow Sphere Composites.
2. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, the volume ratio that it is characterized in that the ammoniacal liquor that the polyacrylic quality described in step 1 and mass percent are 25%～28% is 1g:(14～15) mL.
3. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, the volume ratio that it is characterized in that the polyacrylic quality described in step 1 and dehydrated alcohol is 1g:300mL.
4. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, is characterized in that the volume ratio of the tetraethoxy described in step 1 and polyacrylic quality are 7.5mL:1g.
5. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, is characterized in that the silane coupling agent described in step 2 is 3-aminopropyl trimethoxysilane.
6. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, is characterized in that the nanometer SiO described in step 2
2the mass ratio of hollow spherical powder and silane coupling agent is 1:0.05.
7. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, is characterized in that the nanometer SiO described in step 2
2the quality of hollow spherical powder and N, the volume ratio of N '-N,N-DIMETHYLACETAMIDE is 1g:(34～586) mL.
8. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, is characterized in that the nanometer SiO described in step 2
2the mass ratio of hollow spherical powder and 4,4'-diaminodiphenyl ether is 1:(3～52).
9. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, it is characterized in that electrostatic spinning described in step 3 is the DT-200 type electrostatic spinning machine that adopts Dalian Ding Tong Science and Technology Ltd. to produce, in spinning voltage, be 30kv, receiving angle is 90 °, receiving range is 15～20cm, and shower nozzle diameter is 1.3mm, and syringe fltting speed is 0.0125mm/min, X-axis sweep velocity is 100mm/min, carries out spinning 2h.
10. according to claim 1 a kind of based on polyimide matrix nanometer SiO
2the preparation method of Hollow Sphere Composites, is characterized in that the gradient increased temperature imidization concrete operations described in step 4 are as follows: first surface is covered with to three layers of nanometer SiO
2the glass of hollow ball/Polyamic Acid Film is warming up to 80 ℃ from room temperature, and in temperature, be to keep 30min under the condition of 80 ℃, again temperature is warming up to 120 ℃ by 80 ℃, and in temperature, be to keep 30min under the condition of 120 ℃, then temperature is warming up to 150 ℃ by 120 ℃, in temperature, be to keep 30min under the condition of 150 ℃, again temperature is warming up to 180 ℃ by 150 ℃, in temperature, be to keep 30min under the condition of 180 ℃, then temperature is warming up to 220 ℃ by 180 ℃, in temperature, be to keep 30min under the condition of 220 ℃, then temperature is warming up to 250 ℃ by 220 ℃, in temperature, be to keep 30min under the condition of 250 ℃, finally temperature is warming up to 300 ℃ by 250 ℃, in temperature, be to keep 30min under the condition of 300 ℃.
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