CN103483608B - The organic-silicon-modified PI/SiO of low thermal coefficient of expansion 2the preparation method of hybrid film - Google Patents
The organic-silicon-modified PI/SiO of low thermal coefficient of expansion 2the preparation method of hybrid film Download PDFInfo
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Abstract
The invention discloses the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion
2the preparation method of hybrid film, comprises step: 1) epoxy silane coupling and aromatic diamine are reacted fully in a solvent; 2) add aromatic diamine in the reaction system upwards walked, aromatic dianhydride, tetraethoxy carry out polyreaction and obtain organic-silicon-modified polyamic acid solution; 3) the organic-silicon-modified polyamic acid solution dilution upper step obtained, then be coated on supporter, baking obtains film; 4) heat up film dehydrated crosslinking, obtained product.The film thermal coefficient of expansion prepared by the present invention is low, and preparation method can control homogeneity and the accuracy of reaction well, and experimental period is short, and technique is simple, is applicable to suitability for industrialized production.
Description
Technical field
The present invention relates to the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion
2the preparation method of hybrid film.
Background technology
Polyimide (PI) film is owing to having the over-all propertieies such as excellent thermotolerance, electrical property, mechanical property and physicals, be widely used in Aeronautics and Astronautics, electrically, the high-technology field such as microelectronics and automobile, and demand cumulative year after year.On world market, Kapton is mainly used in the base material of the flexible copper-clad paper tinsel in flexible printed-circuit board.The Kapton of flexible copper-clad paper tinsel has very high requirement to its hot expansibility.Macromolecular material is compared with inorganic materials, and thermotolerance is poor, and thermal expansivity (CET) is also much bigger.Kapton with Copper Foil along with its dimensional change degree of change of temperature is different, make PI copper-clad plate in manufacture and use procedure, the easy phenomenon occurring peeling off, crackle even ruptures, the extreme influence performance of product, so require that the Kapton of flexible printed-circuit board must have the thermal expansivity close with Copper Foil.
The over-all properties that polyimide/silicon dioxide hybrid material can improve polyimide is effectively prepared by sol-gel method.The bond energy of the Si-O in silicon-dioxide is high, has extremely low thermal expansivity, can form the network structure of IPN in organic matrix, so the thermotolerance of polyimide can be made to improve, thermal expansivity reduces.And PI has high thermal stability and high glass-transition temperature, contribute to stable with the inorganic silicon dioxide network of nano-size dispersion, and silicon-dioxide is dispersed in PI matrix resin as reinforcing particles, the over-all properties of polyimide/inorganic matrix material uniqueness will be given.
In the preparation process of polyimide/silicon dioxide hybrid film, add the interface compatibility that coupling agent can improve organic phase and inorganic phase, inorganic particulate size is reduced, distribute more even, thus the light transmission of hybrid film, surface property, mechanical property, thermal characteristics and electrical property are more obviously improved.Will consider the reactable of coupling agent and two-phase on coupling agent is selected, therefore the general silane coupling agent selected containing amino or epoxy group(ing), the control of addition is also extremely important simultaneously.
For this performance of thermal expansivity, the thermal expansivity of pure Kapton is higher, the method of usually carrying out hybrid modification to Kapton is then add in system by organosilicon with the state of collosol and gel, this kind of method brings large water gaging to system, needs a kind of new method of modifying badly.
Summary of the invention
The object of the present invention is to provide the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion
2the preparation method of hybrid film.
The technical solution used in the present invention is:
The organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion
2the preparation method of hybrid film, comprises step:
1) epoxy silane coupling and aromatic diamine are reacted in a solvent fully;
2) add aromatic diamine in the reaction system upwards walked, aromatic dianhydride, tetraethoxy carry out polyreaction and obtain organic-silicon-modified polyamic acid solution;
3) the organic-silicon-modified polyamic acid solution dilution upper step obtained, then be coated on supporter, baking obtains film;
4) heat up film dehydrated crosslinking, obtained product.
Aromatic diamine used in step 1) and step 2) in the mol ratio of aromatic diamine used be 3 ~ 12:100.
Step 1) and step 2) in the total amount of aromatic diamine used and step 2) in aromatic dianhydride mol ratio used be 1.
Step 2) in, the consumption of tetraethoxy is 2% ~ 8% of aromatic dianhydride molar weight.
In step 1), temperature of reaction is 20 ~ 30 DEG C, and the time of reaction is 2 ~ 8 hours; Step 2) in, temperature of reaction is 30 ~ 40 DEG C, and the reaction times is 4 ~ 6 hours.
In step 3), being coated to the thickness that supporter is formed is 10 ~ 50 μm; The temperature of baking is 120 ~ 145 DEG C, and the time of baking is 4 ~ 10min; In step 4), the program of the dehydration that heats up is: rise to 320 ~ 360 DEG C with the temperature rise rate of 20-22 DEG C/min, stops 5 ~ 10min, then cool to room temperature.
Described epoxy silane coupling is γ-(2,3-glycidoxy) propyl trimethoxy silicane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, at least one in 3-(2,3 epoxy third oxygen) hydroxypropyl methyl diethoxy silane.
Described aromatic diamine is at least one in 4,4-diaminodiphenyl oxide, Ursol D, mphenylenediamine, 4,4'-diaminodiphenylmethane.
Described aromatic dianhydride is at least one in pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydrides, 3,3', 4,4'-diphenyl ether tetraformic dianhydrides.
In step 3), the viscosity after described organic-silicon-modified polyamic acid solution dilution is 1600 ~ 1700Pas.
The invention has the beneficial effects as follows: substitute small portion diamines and two anhydride reactants with the diamine monomer of epoxy silane coupling modification, then add tetraethoxy and carry out hydridization, the SiO in prepared polyimide/silicon dioxide hybrid film
2particle diameter, at Nano grade, is uniformly dispersed in polyimide matrix, and thermal expansivity is 35.0 × 10
-6k
-1below.
Silane coupling agent is incorporated on the molecular chain of PI by the diamine monomer of epoxy silane coupling modification, as the bridge of PI molecular chain and tetraethoxy, the silicone hydroxyl formed after epoxy silane coupling hydrolysis, can with teos hydrolysis after silicone hydroxyl generation condensation reaction, make tetraethoxy be condensed into SiO in coupling agent one end
2particle, epoxy radicals silicone hydride is coupled at PI molecular chain and SiO
2erect between particle " molecular bridge ", effectively improve PI and SiO
2interfacial combined function between particle, makes the SiO in hybrid film
2particle can more uniformly be dispersed in PI matrix, makes hybrid film possess more excellent over-all properties.
Tetraethoxy and monomer are added reaction system by preparation method that the present invention proposes jointly, utilize the micro-moisture come from solvent, monomer, make teos hydrolysis, not only avoid and be routinely added to sol-gel state silicon-dioxide brings large water gaging drawback to system, and can be good at removing the water in reaction system, make polycondensation carry out more thorough, molecular weight of product is larger, and better guarantee is acquired can better film.
The preparation method that the present invention proposes can control homogeneity and the accuracy of reaction well, and experimental period is short, and technique is simple, is applicable to suitability for industrialized production.
accompanying drawing illustrates:
Fig. 1 is that the section SEM of the product of embodiment 1 schemes.
Fig. 2 is that the section SEM of the product of embodiment 2 schemes.
Embodiment
The organic-silicon-modified PI/SiO of low thermal coefficient of expansion
2the preparation method of hybrid film, concrete preparation process is as follows:
1) join in organic solvent by aromatic diamine, control temperature, at 20 ~ 30 DEG C, under agitation dissolves, and adds epoxy silane coupling, keeps temperature and stirring, reacts 2 ~ 8 hours;
2) in the system of step 1), add aromatic diamine, control temperature 20 ~ 30 DEG C, after stirring and dissolving, add aromatic dianhydride, then add tetraethoxy, control temperature is 30 ~ 40 DEG C, keep whipped state, react and obtain organic-silicon-modified polyamic acid resin solution after 4 ~ 6 hours;
3) by above-mentioned steps 2) in organic-silicon-modified polyamic acid resin solution be diluted with an organic solvent to be applicable to coating viscosity, after froth breaking on clean supporter plastic film mulch, controlling diaphragm thickness is 10 ~ 50 μm, in 120 ~ 145 DEG C of baking 4 ~ 10min film forming, film is taken off from supporter, is fixed on nail frame, rises to 320 ~ 360 DEG C with the temperature rise rate of 20 DEG C/min, stop 5 ~ 10min, then cool to room temperature obtains silicone-modified polyimides/SiO 2 hybrid film.
Wherein, in step 1), the amount ratio of aromatic diamine and organic solvent is (0.003-0.01) mol:250ml; The mol ratio of aromatic diamine and epoxy silane coupling is 2-1:1, preferably, is 1:1; Aromatic diamine used in step 1) and step 2) in the mol ratio of aromatic diamine used be 3 ~ 12:100; Step 1) and step 2) in the total amount of aromatic diamine used and step 2) in aromatic dianhydride mol ratio used be 1; Step 2) in, the consumption of tetraethoxy is 2% ~ 8% of aromatic dianhydride molar weight.
Step 2) in, the viscosity of the organic-silicon-modified polyamic acid solution of gained is 2800 ~ 3200Pa ﹒ s.
In step 3), the viscosity after described organic-silicon-modified polyamic acid resin solution dilution is 1600 ~ 1700Pas.
In step 3), the method for described froth breaking is for vacuumizing, and supporter is preferably steel plate.
Step 1) and 3) in, described organic solvent is the one in toluene, dimethylbenzene, DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone.
Step 1) and step 2) carry out under protective atmosphere.
Described epoxy silane coupling is γ-(2,3-glycidoxy) propyl trimethoxy silicane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, at least one in 3-(2,3 epoxy third oxygen) hydroxypropyl methyl diethoxy silane; Described aromatic diamine is at least one in 4,4-diaminodiphenyl oxide, Ursol D, mphenylenediamine, 4,4'-diaminodiphenylmethane; Described aromatic dianhydride is at least one in pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydrides, 3,3', 4,4'-diphenyl ether tetraformic dianhydrides.
Below in conjunction with specific embodiment, the present invention is described further:
comparative example:
Under nitrogen atmosphere protection, 0.1mol4,4-diaminodiphenyl oxide is joined 250mlN; in dinethylformamide, control temperature 30 DEG C, after stirring and dissolving; add 0.1mol pyromellitic acid anhydride, constant temperature stirs, and reacts after 4 hours and obtains the polyamic acid resin solution that viscosity is 2350Pa ﹒ s.By polyamic acid resin solution N, it is 1650Pa ﹒ s that dinethylformamide is diluted to viscosity, after froth breaking on clean steel plate plastic film mulch, the thickness of controlling diaphragm is 30 μm, in 150 DEG C of baking 5min film forming, is taken off by film from steel plate, be fixed on nail frame, rise to 320 DEG C with the temperature rise rate of 20 DEG C/min by 150 DEG C, at 320 DEG C, stop 10min, then cool to room temperature obtains Kapton.
The thermal expansivity (CET) of this Kapton is 41.4 × 10
-6k
-1.
embodiment 1:
Under nitrogen atmosphere protection, by 0.003mol4,4-diaminodiphenyl oxide joins 250mlN, in N-N,N-DIMETHYLACETAMIDE, and control temperature 20 DEG C, after stirring and dissolving, add γ-(2,3-glycidoxy) propyl trimethoxy silicane of equimolar amount, constant temperature stirs, react the N,N-dimethylacetamide solution obtaining organic-silicon-modified aromatic diamine monomer after 2 hours;
Under nitrogen atmosphere protection, to the N of above-mentioned organic-silicon-modified aromatic diamine monomer, in N-dimethylacetamide solution, add 0.1mol4,4-diaminodiphenyl oxide, control temperature 20 DEG C, after stirring and dissolving, add 0.103mol pyromellitic acid anhydride, then add 0.00206mol tetraethoxy, control temperature 30 DEG C, stirring reaction obtains the organic-silicon-modified polyamic acid resin solution that viscosity is 2800Pa ﹒ s after 4 hours;
By organic-silicon-modified polyamic acid resin solution N, it is 1650Pa ﹒ s that N-N,N-DIMETHYLACETAMIDE is diluted to viscosity, after froth breaking on clean steel plate plastic film mulch, the thickness of controlling diaphragm is 10 μm, in 120 DEG C of baking 4min film forming, is taken off by film from steel plate, be fixed on nail frame, rise to 320 DEG C with the temperature rise rate of 20 DEG C/min by 120 DEG C, at 320 DEG C, stop 5min, then cool to room temperature obtains silicone-modified polyimides/SiO 2 hybrid film.
SiO in this silicone-modified polyimides/SiO 2 hybrid film
2particle diameter, at Nano grade, is uniformly dispersed in polyimide matrix, and thermal expansivity (CET) is 29.4 × 10
-6k
-1.
The section SEM being the product of embodiment 1 as Fig. 1 schemes.
embodiment 2:
Under helium atmosphere protection, 0.01mol Ursol D is joined 250mlN, in dinethylformamide, control temperature 30 DEG C, after stirring and dissolving, adds the 2-(3 of equimolar amount, 4-epoxy cyclohexane base) ethyl trimethoxy silane, constant temperature stirs, and reacts the DMF solution obtaining organic-silicon-modified aromatic diamine monomer after 8 hours;
Under helium atmosphere protection, to the N of above-mentioned organic-silicon-modified aromatic diamine monomer, in dinethylformamide solution, add 0.1mol Ursol D, control temperature 30 DEG C, after stirring and dissolving, add 0.11mol bibenzene tetracarboxylic dianhydride, add 0.0088mol tetraethoxy again, control temperature 40 DEG C, stirring reaction obtains the organic-silicon-modified polyamic acid resin solution that viscosity is 3200Pa ﹒ s after 6 hours;
By organic-silicon-modified polyamic acid resin solution N, it is 1600Pa ﹒ s that dinethylformamide is diluted to viscosity, after froth breaking on clean steel plate plastic film mulch, the thickness of controlling diaphragm is 50 μm, in 145 DEG C of baking 10min film forming, is taken off by film from steel plate, be fixed on nail frame, rise to 360 DEG C with the temperature rise rate of 20 DEG C/min by 145 DEG C, at 360 DEG C, stop 10min, then cool to room temperature obtains silicone-modified polyimides/SiO 2 hybrid film.
SiO in this silicone-modified polyimides/SiO 2 hybrid film
2particle diameter, at Nano grade, is uniformly dispersed in polyimide matrix, and thermal expansivity (CET) is 33.6 × 10
-6k
-1.
The section SEM being the product of embodiment 2 as Fig. 2 schemes.
embodiment 3:
Under argon gas atmosphere protection, 0.008mol mphenylenediamine is joined in 250ml toluene, control temperature 25 DEG C, after stirring and dissolving, add the 3-(2 of equimolar amount, 3 epoxy third oxygen) hydroxypropyl methyl diethoxy silane, constant temperature stirs, and reacts the toluene solution obtaining organic-silicon-modified aromatic diamine monomer after 6 hours;
Under argon gas atmosphere protection, to in the toluene solution of above-mentioned organic-silicon-modified aromatic diamine monomer, add 0.1mol mphenylenediamine, control temperature 25 DEG C, after stirring and dissolving, add 0.108mol3,3,4,4-benzophenone tetracarboxylic dianhydride, add 0.00648mol tetraethoxy again, control temperature 35 DEG C, stirring reaction obtains the organic-silicon-modified polyamic acid resin solution that viscosity is 2950Pa ﹒ s after 5 hours;
Be 1700Pa ﹒ s by organic-silicon-modified polyamic acid resin solution dilution with toluene to viscosity, after froth breaking on clean steel plate plastic film mulch, the thickness of controlling diaphragm is 30 μm, in 135 DEG C of baking 8min film forming, film is taken off from steel plate, is fixed on nail frame, rises to 350 DEG C with the temperature rise rate of 20 DEG C/min by 135 DEG C, at 350 DEG C, stop 8min, then cool to room temperature obtains silicone-modified polyimides/SiO 2 hybrid film.
SiO in this silicone-modified polyimides/SiO 2 hybrid film
2particle diameter, at Nano grade, is uniformly dispersed in polyimide matrix, and thermal expansivity (CET) is 30.7 × 10
-6k
-1.
embodiment 4:
Under helium atmosphere protection, by 0.005mol4,4'-diaminodiphenylmethane joins in 250ml dimethylbenzene, control temperature 20 DEG C, after stirring and dissolving, adds the 3-(2 of 0.0025mol, 3 epoxy third oxygen) γ-(2 of hydroxypropyl methyl diethoxy silane and 0.0025mol, 3-glycidoxy) propyl trimethoxy silicane, constant temperature stirs, and reacts the xylene solution obtaining organic-silicon-modified aromatic diamine monomer after 5 hours;
Under helium atmosphere protection, in the xylene solution of above-mentioned organic-silicon-modified aromatic diamine monomer, add 0.1mol4,4'-diaminodiphenylmethane, control temperature 25 DEG C, after stirring and dissolving, adds 0.105mol3,3', 4,4'-diphenyl ether tetraformic dianhydride, then add 0.0042mol tetraethoxy, control temperature 40 DEG C, stirring reaction obtains the organic-silicon-modified polyamic acid resin solution that viscosity is 2920Pa ﹒ s after 4 hours;
It is 1620Pa ﹒ s that organic-silicon-modified polyamic acid resin solution dimethylbenzene is diluted to viscosity, after froth breaking on clean steel plate plastic film mulch, the thickness of controlling diaphragm is 40 μm, in 125 DEG C of baking 9min film forming, film is taken off from steel plate, is fixed on nail frame, rises to 340 DEG C with the temperature rise rate of 20 DEG C/min by 125 DEG C, at 340 DEG C, stop 7min, then cool to room temperature obtains silicone-modified polyimides/SiO 2 hybrid film.
SiO in this silicone-modified polyimides/SiO 2 hybrid film
2particle diameter, at Nano grade, is uniformly dispersed in polyimide matrix, and thermal expansivity (CET) is 31.9 × 10
-6k
-1.
embodiment 5:
Under nitrogen atmosphere protection, by 0.006mol4,4-diaminodiphenyl oxide joins in 250mlN-methyl-2-pyrrolidone, control temperature 30 DEG C, after stirring and dissolving, adds the 2-(3 of 0.002mol, 4-epoxy cyclohexane base) γ-(2 of ethyl trimethoxy silane and 0.004mol, 3-glycidoxy) propyl trimethoxy silicane, constant temperature stirs, and reacts the N-Methyl pyrrolidone solution obtaining organic-silicon-modified aromatic diamine monomer after 7 hours;
Under nitrogen atmosphere protection, to in the N-Methyl pyrrolidone solution of above-mentioned organic-silicon-modified aromatic diamine monomer, add 0.05mol4,4-diaminodiphenyl oxide and 0.05mol Ursol D, control temperature 25 DEG C, after stirring and dissolving, add 0.056mol pyromellitic acid anhydride and 0.05mol bibenzene tetracarboxylic dianhydride, add 0.00742mol tetraethoxy again, control temperature 35 DEG C, stirring reaction obtains the organic-silicon-modified polyamic acid resin solution that viscosity is 2860Pa ﹒ s after 4.5 hours;
It is 1650Pa ﹒ s that organic-silicon-modified polyamic acid resin solution N-Methyl pyrrolidone is diluted to viscosity, after froth breaking on clean steel plate plastic film mulch, the thickness of controlling diaphragm is 35 μm, in 130 DEG C of baking 8min film forming, film is taken off from steel plate, is fixed on nail frame, rises to 330 DEG C with the temperature rise rate of 20 DEG C/min by 130 DEG C, at 330 DEG C, stop 6min, then cool to room temperature obtains silicone-modified polyimides/SiO 2 hybrid film.
SiO in this silicone-modified polyimides/SiO 2 hybrid film
2particle diameter, at Nano grade, is uniformly dispersed in polyimide matrix, and thermal expansivity (CET) is 27.5 × 10
-6k
-1.
Claims (9)
1. the organic-silicon-modified PI/SiO of low thermal coefficient of expansion
2the preparation method of hybrid film, is characterized in that: comprise step:
1) epoxy silane coupling and aromatic diamine are reacted in a solvent fully;
2) add aromatic diamine in the reaction system upwards walked, aromatic dianhydride, tetraethoxy carry out polyreaction and obtain organic-silicon-modified polyamic acid solution;
3) the organic-silicon-modified polyamic acid solution dilution upper step obtained, then be coated on supporter, baking obtains film;
4) heat up film dehydrated crosslinking, obtained product;
Described epoxy silane coupling is γ-(2,3-glycidoxy) propyl trimethoxy silicane, 2-(3,4-epoxy cyclohexane base) ethyl trimethoxy silane, at least one in 3-(2,3-epoxy third oxygen) hydroxypropyl methyl diethoxy silane.
2. the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion according to claim 1
2the preparation method of hybrid film, is characterized in that: aromatic diamine used in step 1) and step 2) in the mol ratio of aromatic diamine used be 3 ~ 12:100.
3. the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion according to claim 1
2the preparation method of hybrid film, is characterized in that: step 1) and step 2) in the total amount of aromatic diamine used and step 2) in aromatic dianhydride mol ratio used be 1.
4. the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion according to claim 1
2the preparation method of hybrid film, is characterized in that: step 2) in, the consumption of tetraethoxy is 2% ~ 8% of aromatic dianhydride molar weight.
5. the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion according to claim 1
2the preparation method of hybrid film, is characterized in that: in step 1), and temperature of reaction is 20 ~ 30 DEG C, and the time of reaction is 2 ~ 8 hours; Step 2) in, temperature of reaction is 30 ~ 40 DEG C, and the reaction times is 4 ~ 6 hours.
6. the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion according to claim 1
2the preparation method of hybrid film, is characterized in that: in step 3), and being coated to the thickness that supporter is formed is 10 ~ 50 μm; The temperature of baking is 120 ~ 145 DEG C, and the time of baking is 4 ~ 10min; In step 4), the program of the dehydration that heats up is: rise to 320 ~ 360 DEG C with the temperature rise rate of 20-22 DEG C/min, stops 5 ~ 10min, then cool to room temperature.
7. the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion according to claim 1
2the preparation method of hybrid film, is characterized in that: described aromatic diamine is at least one in 4,4-diaminodiphenyl oxide, Ursol D, mphenylenediamine, 4,4'-diaminodiphenylmethane.
8. the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion according to claim 1
2the preparation method of hybrid film, is characterized in that: described aromatic dianhydride is at least one in pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, 3,3,4,4-benzophenone tetracarboxylic dianhydrides, 3,3', 4,4'-diphenyl ether tetraformic dianhydrides.
9. the organic-silicon-modified PI/SiO of a kind of low thermal coefficient of expansion according to claim 1
2the preparation method of hybrid film, is characterized in that: in step 3), and the viscosity after described organic-silicon-modified polyamic acid solution dilution is 1600 ~ 1700Pas.
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| CN107286653A (en) * | 2017-07-17 | 2017-10-24 | 安徽国风塑业股份有限公司 | A kind of preparation method of high-performance low thermal expansion coefficient polyimide film |
| CN108623828B (en) * | 2018-05-30 | 2020-02-18 | 四川大学 | Method for preparing inorganic nanoparticle/aromatic polyimide composite film and prepared composite film |
| CN110698682B (en) * | 2019-09-27 | 2022-02-22 | 武汉华星光电半导体显示技术有限公司 | Polyimide composite material, preparation method and application thereof |
| CN111808306B (en) * | 2020-06-16 | 2023-04-07 | 浙江中科玖源新材料有限公司 | Polyimide film with low thermal expansion coefficient and preparation method thereof |
| CN112011074A (en) * | 2020-07-29 | 2020-12-01 | 浙江中科玖源新材料有限公司 | Organic silicon modified polyimide film and preparation method thereof |
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| "偶联剂对聚酰亚胺/SiO2杂化膜性能的影响";李海瑞等;《化学工程》;20080131;第36卷(第1期);第52页摘要 * |
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