CN105153699A - Preparation method of hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film - Google Patents
Preparation method of hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film Download PDFInfo
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Abstract
The invention provides a preparation method of a hyper branched copolymerized polyimide/zinc oxide (ZnO) hybrid insulated film, and the method comprises the following steps: preparing a hyper branched copolymerized polyamide acid film: employing 3,3',4,4'-tetracarboxydiphthalic ether dianhydride, triamine monomer 1,3,5-tri[4-(4-aminophenoxy)phenyl]benzene and 4,4'-diaminodiphenyl ether three monomers as raw materials, carrying out condensation polymerization according to a mole proportion 1:0.4:0.5, and obtaining a yellow viscous transparent solution; dropping the obtained solution on a glass plate with a silica gel frame, and obtaining the hyper branched copolymerized polyamide acid film after drying; completing imidization of the hyper branched copolymerized polyamide acid film by one step and forming zinc oxide nanoparticles: preparing a zinc chloride solution, totally soaking the hyper branched copolymerized polyamide acid film in a zinc chloride solution, after completing soaking, taking the hyper branched copolymerized polyamide acid film out for washing; and baking for preparing the product. By means of hybrid of hyper branched polyimide and nanometer zinc oxide, the dielectric constant is reduced and insulating property of the material is added, simultaneously heat resistance and mechanical performance are improved, thereby meeting requirements of different electronic components for materials.
Description
Technical field
The present invention relates to field of polymer material preparing technology, be specifically related to a kind of preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film.
Background technology
The develop rapidly of modern science and technology is had higher requirement to the kind of material and performance, can be met the demand of some property by the hydridization of material.The feature of hybrid material is the advantage combining various component, and plays multi-functional effect.Not only can retain its excellent properties to the suitable hydridization of polyimide, the characteristic that some are brand-new can also be had, to adapt to the requirements at the higher level of development of modern industry to polyimide performance.Polyimide can move by blocks electrons effectively, prevent chemical corrosion from strengthening the moisture resistant ability of electron device and mechanical property etc., so polyimide can have a wide range of applications in electrotechnical, electronic as the insulating material of key, in conventional electric insulation, occupy unique status.Modern microelectronic industry is in order to reach higher integrated level, and require that chip size is more and more less, in chip, the time of lag of Signal transmissions also can correspondingly increase, and this time of lag is directly proportional to the specific inductivity of interlayer dielectic.In order to improve the transmission speed of signal, the specific inductivity of interlayer dielectic must be reduced to 2.0 ~ 2.6, the specific inductivity of usual polyimide material is 3.0 ~ 3.5, is difficult to meet this requirement.
In order to reduce the specific inductivity of polyimide, among existing research, more obtain matrix material by the method blended with linear polyimide at present, and this kind of method is often because the small-size effect of blend is more easily reunited, the matrix material obtained is made cannot effectively to improve its dielectric properties.
Summary of the invention
The object of this invention is to provide a kind of preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film, its specific inductivity is reduced by super-branched polyimide and nano zinc oxide hybridization, increase the insulativity of product, its resistance toheat and mechanical property can be improved simultaneously, meet the requirement of different electronic component to material.
To achieve these goals, the technical solution used in the present invention is as follows:
A preparation method for hyperbranched copolyimide/zinc oxide hybridization insulation film, comprises the steps:
1) preparation of hyperbranched copolyamide sorrel (co-HBPAA): adopt 3, 3 ', 4, 4 '-diphenyl ether tetraformic dianhydride (ODPA), Triamine monomer 1, 3, 5-tri-[4-(4-amido phenoxy group) phenyl] benzene (TAPOPB) and 4, 4 '-diaminodiphenyl oxide (ODA), three kinds of monomers are raw material, molar ratio with 1: 0.4: 0.5 carries out polycondensation: first use METHYLPYRROLIDONE (NMP) to dissolve 3, 3 ', 4, 4 '-diphenyl ether tetraformic dianhydride, until completely dissolved, slowly be added drop-wise to and be equipped with 1, 3, 5-tri-[4-(4-amido phenoxy group) phenyl] benzene and 4, polycondensation is carried out in the METHYLPYRROLIDONE solution of 4 '-diaminodiphenyl oxide, obtain the clear solution of clear yellow viscous, then, the solution obtained is dropped on the sheet glass with silica gel frame, then put into vacuum drying oven dry (to remove residual solvent), obtain hyperbranched copolyamide sorrel, peel off from sheet glass for subsequent use,
2) step completes the imidization of hyperbranched copolyamide sorrel and the formation of zinc oxide (ZnO) nanoparticle: configuration zinc chloride (ZnCl
2) solution, then hyperbranched copolyamide sorrel is fully immersed in liquor zinci chloridi, has soaked the hyperbranched copolyamide sorrel of rear taking-up, with deionized water rinsing (to remove the ZnCl remained on film
2solution); Toast with putting into baking oven after clip fixed film (preventing film from occurring in hot imidization process curling), a step completes the hyperbranched imidization of copolyamide sorrel and the formation of zinc oxide nano-particle, obtained product.
According to above scheme, described 3,3 ', 4, the dropping of 4 '-diphenyl ether tetraformic dianhydride carries out under the condition of nitrogen protection and ice-water bath, and time for adding is 1h, and described polycondensation is successive reaction 12h in ice-water bath.
According to above scheme, the drying temperature of described vacuum drying oven drying is 60 DEG C, and time of drying is 12h.
According to above scheme, the concentration of described liquor zinci chloridi is 2mol/L, when configuring, also adds appropriate concentrated hydrochloric acid until solution just clear, to prevent due to ZnCl
2the water-soluble rear hydrolysis of particle produces zinc hydroxide Zn (OH)
2flocks, causes Zn
2+concentration reduces.
According to above scheme, described soak time is 4h.
According to above scheme, described deionized water rinsing number of times is 3 times.
According to above scheme, the detailed process of described baking is: at the temperature of 150 DEG C, 200 DEG C, 250 DEG C and 300 DEG C, toast 1h respectively.
The invention has the beneficial effects as follows:
1) the present invention's sour and liquor zinci chloridi generation ion-exchange by the presoma ultrabranching polyamide of super-branched polyimide, each carboxylic acid provides access point for zine ion, nano zine oxide is obtained after a step thermal treatment, by on the carbonyl of physical adsorption on imide ring, effectively reduce the reunion of nanoparticle, in matrix super-branched polyimide structure, there is a lot of cavity structure simultaneously, add the composition of air in material, so the two comprehensively improves dielectric properties and the insulativity of hybridized film, reduce the specific inductivity of material;
2) in the present invention, the introducing of nanoparticle improves thermal characteristics and the mechanical property of material, improves the dimensional stability of material, is more suitable for the application in microelectronic.
Accompanying drawing explanation
Fig. 1 is co-HBPI/ZnO hybrid film synthetic route schematic diagram of the present invention;
Fig. 2 is that a step of the present invention prepares co-HBPI/ZnO hybrid film process schematic;
Fig. 3 is energy dispersion x-ray (EDX) the energy spectrogram of product of the present invention;
Fig. 4 is pure co-HBPI film and the thermogravimetric analysis of product of the present invention under air atmosphere (TGA) graphic representation;
Fig. 5 is the stress-strain curve of pure co-HBPI film and product of the present invention;
Fig. 6 is scanning electron microscope (SEM) figure of the surface contact angle performance of pure co-HBPI film and product of the present invention;
Fig. 7 is the change curve of specific inductivity with frequency of pure co-HBPI film and product of the present invention.
Embodiment
Below in conjunction with accompanying drawing and embodiment, technical scheme of the present invention is described.
The invention provides a kind of preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film, comprise the steps:
1) preparation of hyperbranched copolyamide sorrel (co-HBPAA): adopt ODPA, TAPOPB and ODA tri-kinds of monomers to be raw material, molar ratio with 1: 0.4: 0.5 carries out polycondensation (as shown in Figure 1): dissolve ODPA with 10mlNMP, until completely dissolved, at N
2under atmosphere in ice-water bath, be slowly added drop-wise in 1h in two mouthfuls of flasks of the nmp solution that 10mlTAPOPB and ODA is housed with dropping funnel, dropwise, continue to react 12h in ice-water bath, obtain the clear solution of clear yellow viscous; Then, the solution obtained is dropped on the sheet glass with silica gel frame, put into 60 DEG C of vacuum drying oven 12h to remove residual solvent, obtain hyperbranched copolyamide sorrel, peel off from sheet glass for subsequent use;
2) step completes the imidization of co-HBPAA and the formation of ZnO nanoparticle: the liquor zinci chloridi first configuring 2mol/L, and adds several concentrated hydrochloric acids until solution just clear; The hyperbranched copolyamide sorrel of preparation is fully immersed in 4h in the liquor zinci chloridi configured, then takes out film, repeatedly rinse 3 times with deionized water, to remove the ZnCl remained on film
2solution; Then, baking oven is put into clip fixed film, at 150 DEG C, 200 DEG C, 1h is dried respectively at the temperature of 250 DEG C and 300 DEG C, one step completes the imidization of co-HBPAA and the formation of ZnO nanoparticle, and system obtains product hyperbranched copolyimide/zinc oxide hybridization insulation film (co-HBPI/ZnO hybrid film) (process schematic as shown in Figure 2).
In order to analyze the distribution of ZnO in co-HBPI film quantitatively, the measuring EDX collection of illustrative plates (see Fig. 3) of product of the present invention.Result shows, the content recording Zn is 1.46%, illustrates that ZnO truly has and is introduced into.
Thermal performance test: the thermal characteristics of product of the present invention has been undertaken characterizing (see Fig. 4) by TGA.Table 1 lists the thermal weight loss temperature of pure co-HBPI film and product of the present invention 5%, 10%.As can be seen from Figure 4, along with the introducing of ZnO particle, the thermostability of hybrid film is improved slightly, but the amplitude improved is not very large.In general, the interface interaction power between particle and matrix affects the thermal stability of hybrid material largely.ZnO particle is mainly adsorbed on the surface of polyimide film with Intermolecular Forces, so the space structure of co-HBPI molecule changes very little, only add the gravitation of ZnO to molecular chain on surface, result in the raising slightly for hybrid film thermal characteristics in macro manifestations.It can also be seen that from Fig. 4, in air atmosphere, when being warmed up to 800 DEG C, the residual volume of pure co-HBPI film is zero, and the residual volume of product of the present invention is probably 1.81%, is the content of ZnO, roughly conforms to the content of the Zn of EDX gamma spectrometry.
The weightless temperature of table 1 pure co-HBPI film and product of the present invention 5%, 10%
Measuring mechanical property: different from common linear polyimides, super-branched polyimide is because its global molecular structure lacks physical entanglement and is considered to have relatively poor mechanical property.In the present invention, copolyimide film successfully introduces ZnO particle, improve tensile strength and the elongation at break of material.As can be seen from Table 2, along with the loading of ZnO, tensile strength is elevated to 103.41MPa from 96.14MPa, and elongation at break is elevated to 14.60% (as shown in Fig. 5 curvilinear trend) from 10.51%.ZnO particle improves the mechanical property of co-HBPI film mainly owing to the interaction force between ZnO particle and matrix, contributes to the transmission of stress.For whole system, ZnO particle can good absorption energy transmit stress, reduces the material damage produced because of stress concentration, thus improves the mechanical property of material.
The measuring mechanical property result of table 2 pure co-HBPI film product of the present invention
Surface contact angle is tested: be used for measuring the surface contact angle (CA) of film, measures its effect to water quantitatively.Test result shows (see Fig. 6), after being loaded into ZnO particle, the CA value of product of the present invention is reduced to 79.7 ° by 101.5 ° of pure co-HBPI film, namely becomes wetting ability (CA < 90 °) by original hydrophobicity (CA > 90 °).Although SEM figure is after (Fig. 7) show to add ZnO, co-HBPI film becomes coarse by smooth, in theory can the hydrophobicity of reinforcing membrane, and not surface treated nano zine oxide has polarity, and it is hydrophilic nano powder.In addition, nano zine oxide, compared with common zinc oxide, belongs to porous micropowder material, and there is a large amount of hydroxyls with strong polarity on its surface, and its ability absorbed water is stronger, shows certain hydrophilicity simultaneously.Hydroxyl on nano zine oxide is larger to hydrophilic contribution than its roughness brought, so whole hybridized film shows wetting ability.
Dielectric properties are tested: Fig. 7 is the change curve of specific inductivity with frequency of pure co-HBPI film and product of the present invention, and its range of frequency is 50kHz ~ 1000kHz.As shown in Figure 7, the specific inductivity of pure co-HBPI film and product of the present invention has decline in various degree with the increase of test frequency, is 3.01 and 2.61 under the test frequency of 1MHz respectively.Wherein the specific inductivity of pure co-HBPI film is lower in polyimide, major cause is that dissaving structure lacks chain entanglement, define a lot of cavity structure in matrix, introduce the air that more specific inductivity are very low, make the specific inductivity of pure co-HBPI film lower than normal linear polyimide; And the introducing of nano-ZnO defines and physical adsorption between matrix and hybrid structure, inhibit the polarized action of material, reduce the specific inductivity of material; Therefore the synergy of two aspects makes the specific inductivity of product of the present invention have a decline by a relatively large margin than pure co-HBPI film, substantially reaches the insulating requirements in microelectronics industry.
Above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although above-described embodiment is to invention has been detailed description, the person skilled of this area is to be understood that: can modify to the present invention or replace on an equal basis, but any amendment not departing from spirit and scope of the invention all should be encompassed in right of the present invention with local replacement.
Claims (7)
1. a preparation method for hyperbranched copolyimide/zinc oxide hybridization insulation film, is characterized in that, comprise the steps:
1) preparation of hyperbranched copolyamide sorrel: adopt 3, 3 ', 4, 4 '-diphenyl ether tetraformic dianhydride, Triamine monomer 1, 3, 5-tri-[4-(4-amido phenoxy group) phenyl] benzene and 4, 4 '-diaminodiphenyl oxide, three kinds of monomers are raw material, molar ratio with 1: 0.4: 0.5 carries out polycondensation: first dissolve 3 with METHYLPYRROLIDONE, 3 ', 4, 4 '-diphenyl ether tetraformic dianhydride, until completely dissolved, slowly be added drop-wise to and be equipped with 1, 3, 5-tri-[4-(4-amido phenoxy group) phenyl] benzene and 4, polycondensation is carried out in the METHYLPYRROLIDONE solution of 4 '-diaminodiphenyl oxide, obtain the clear solution of clear yellow viscous, then, the solution obtained is dropped on the sheet glass with silica gel frame, then it is dry to put into vacuum drying oven, obtains hyperbranched copolyamide sorrel, peels off for subsequent use from sheet glass,
2) step completes the hyperbranched imidization of copolyamide sorrel and the formation of zinc oxide nano-particle: configuration liquor zinci chloridi, then hyperbranched copolyamide sorrel is fully immersed in liquor zinci chloridi, the hyperbranched copolyamide sorrel of taking-up after immersion completes, with deionized water rinsing; Toast with putting into baking oven after clip fixed film, a step completes the hyperbranched imidization of copolyamide sorrel and the formation of zinc oxide nano-particle, obtained product.
2. the preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film according to claim 1; it is characterized in that; described 3; 3 '; 4; the dropping of 4 '-diphenyl ether tetraformic dianhydride carries out under the condition of nitrogen protection and ice-water bath, and time for adding is 1h, and described polycondensation is successive reaction 12h in ice-water bath.
3. the preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film according to claim 1, is characterized in that, the drying temperature of described vacuum drying oven drying is 60 DEG C, and time of drying is 12h.
4. the preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film according to claim 1, is characterized in that, the concentration of described liquor zinci chloridi is 2mol/L, when configuring, also adds appropriate concentrated hydrochloric acid until solution just clear.
5. the preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film according to claim 1, is characterized in that, described soak time is 4h.
6. the preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film according to claim 1, is characterized in that, described deionized water rinsing number of times is 3 times.
7. the preparation method of hyperbranched copolyimide/zinc oxide hybridization insulation film according to claim 1, is characterized in that, the detailed process of described baking is: at the temperature of 150 DEG C, 200 DEG C, 250 DEG C and 300 DEG C, toast 1h respectively.
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Cited By (11)
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| CN105602248A (en) * | 2016-01-28 | 2016-05-25 | 国网山东省电力公司电力科学研究院 | Polymer insulator material and preparation method thereof |
| CN106083612A (en) * | 2016-06-14 | 2016-11-09 | 湖北大学 | A kind of fluorine-containing Triamine monomer and its preparation method and application |
| CN106519675A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BTDA-type bisphenol-A tetramine branched polyimide resin film and preparation method thereof |
| CN106519670A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA-type BDATHQ branched polyimide resin film and preparation method thereof |
| CN106633869A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA-type BDATHQ branched polyimide resin thin film and preparation method thereof |
| CN107043535A (en) * | 2017-04-25 | 2017-08-15 | 晶锋集团股份有限公司 | A kind of bismuth, manganese, cobalt, zinc oxide polyimide composite film of niobium doping and preparation method thereof |
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| CN112321825A (en) * | 2020-09-27 | 2021-02-05 | 浙江中科玖源新材料有限公司 | Heat-resistant transparent polyimide film and preparation method thereof |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602248A (en) * | 2016-01-28 | 2016-05-25 | 国网山东省电力公司电力科学研究院 | Polymer insulator material and preparation method thereof |
| CN106083612B (en) * | 2016-06-14 | 2018-02-23 | 湖北大学 | A kind of fluorine-containing Triamine monomer and its preparation method and application |
| CN106083612A (en) * | 2016-06-14 | 2016-11-09 | 湖北大学 | A kind of fluorine-containing Triamine monomer and its preparation method and application |
| US10689489B2 (en) | 2016-06-30 | 2020-06-23 | Lg Chem Ltd. | Polyimide-based block copolymer and polyimide-based film comprising the same |
| CN106280440B (en) * | 2016-09-23 | 2018-04-13 | 齐鲁工业大学 | A kind of polymolecularity Polyimide/Nano particle composite film and preparation method thereof |
| CN106519670A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | ODPA-type BDATHQ branched polyimide resin film and preparation method thereof |
| CN106633869A (en) * | 2016-11-04 | 2017-05-10 | 东华大学 | BTDA-type BDATHQ branched polyimide resin thin film and preparation method thereof |
| CN106519675A (en) * | 2016-11-04 | 2017-03-22 | 东华大学 | BTDA-type bisphenol-A tetramine branched polyimide resin film and preparation method thereof |
| CN107043535A (en) * | 2017-04-25 | 2017-08-15 | 晶锋集团股份有限公司 | A kind of bismuth, manganese, cobalt, zinc oxide polyimide composite film of niobium doping and preparation method thereof |
| CN111509176A (en) * | 2020-04-29 | 2020-08-07 | 东莞东阳光科研发有限公司 | Cross-linked polyimide/ceramic composite diaphragm and preparation method thereof |
| CN111509176B (en) * | 2020-04-29 | 2022-12-27 | 东莞东阳光科研发有限公司 | Cross-linked polyimide/ceramic composite diaphragm and preparation method thereof |
| CN112321825A (en) * | 2020-09-27 | 2021-02-05 | 浙江中科玖源新材料有限公司 | Heat-resistant transparent polyimide film and preparation method thereof |
| CN113725553A (en) * | 2021-09-01 | 2021-11-30 | 北京宇程科技有限公司 | Polyimide/zinc oxide composite lithium ion battery diaphragm and preparation method thereof |
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