CN113072700A - Intrinsic black polyimide film with improved mechanical properties and method for preparing the same - Google Patents
Intrinsic black polyimide film with improved mechanical properties and method for preparing the same Download PDFInfo
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Abstract
The present invention relates to an intrinsic black polyimide film having improved mechanical properties and a method for preparing the same. According to the technical scheme provided by the invention, the improved mechanical property and good breakdown-resistant electrical property of the polyimide film can be improved and maintained while the high content of the intrinsic black NDA component is ensured.
Description
Technical Field
The invention relates to the field of organic chemical industry and inorganic chemical industry, relates to a composite material formed by organic/inorganic components, and particularly relates to an intrinsic black polyimide film and a preparation method thereof.
Background
Polyimides (PIs) are one of the high performance materials that have been nationally identified as an important research and breakthrough due to their excellent thermal stability and oxidative stress, chemical resistance, and excellent mechanical and electrical properties. High performance polyimide films have been widely used in gas separations, microelectronics, space devices, integrated electronic circuits, passivation coatings, substrate assemblies, adhesives, composites, and the like.
Among polyimide-related products that have recently received attention, an increasing number of fabrication processes emphasize the manufacture of polyimide thin films that are intrinsically black or intrinsically have light-shielding ability, which do not require the addition of other black substances to receive much attention, and research has been made thereon. For example, chinese patent publication CN109180936A discloses an intrinsic black polyimide film, and a preparation method and use thereof. According to the technical scheme of the patent, the method comprises the following steps of dissolving aromatic diamine monomer in aprotic strong polar solvent, and forming homogeneous solution under stirring; the aromatic diamine monomer is a mixture of 4,4' -diaminodiphenyl ether and 4,4' -diaminodiphenylamine, or 4,4' -diaminodiphenylamine; adding dianhydride monomer and residual aprotic strong polar solvent into the obtained homogeneous phase solution to obtain a reaction system, and reacting at the temperature of 0-35 ℃ for 10-30 hours to obtain polyamic acid solution; and uniformly coating the obtained polyamic acid solution on a clean glass plate, placing the glass plate in a program temperature control drying box, gradually heating and curing according to a program, naturally cooling the program temperature control drying box to room temperature, taking out the glass plate, soaking the glass plate in deionized water, and peeling to obtain the black polyimide film.
The patented technology can realize an intrinsic black polyimide film, but the patented technology cannot ensure that the polyimide film has good mechanical properties, such as tensile resistance and fracture resistance, while meeting the light shielding conditions. This may be due to the use of a 4, 4' -diaminodiphenylamine (NDA) component. However, if a large amount of 4, 4' -diaminodiphenylamine (NDA) component is not used, the intrinsic black color property cannot be achieved.
Therefore, there is a need to provide an intrinsic polyimide film that can ensure good electrical breakdown resistance, and also has good optical shielding and mechanical properties.
Disclosure of Invention
The inventors have found that while the 4, 4' -diaminodiphenylamine (NDA) component imparts an intrinsic black color to the polyimide, it also reduces or degrades the mechanical properties of the film, as the associated test results indicate that the number average molecular weight (Mn) of the intermediate polyamic acid solution (PAA) decreases with increasing NDA content in the polymer. The decrease in the number average molecular weight leads to a decrease in the viscosity of the mixed solution, thereby deteriorating the mechanical properties of the finally heat-synthesized polyimide film.
In order to solve the above problems, in a first aspect of the present invention, there is provided a method for preparing an intrinsic black polyimide film having improved mechanical properties, the method comprising the steps of:
Step 1), mixing nano silicon dioxide particles with a long-chain organic auxiliary agent to obtain a nano silicon dioxide composite filler component, wherein the mass ratio of the nano silicon dioxide particles to the long-chain organic auxiliary agent is 1:1 to 1: 0.1;
a step 2) of mixing 4, 4 '-diaminodiphenyl ether ODA, 4' -diaminodiphenylamine NDA, and the nanosilica composite filler component, wherein the ratio of the amount of the substance of 4, 4 '-diaminodiphenyl ether ODA to the amount of the substance of 4, 4' -diaminodiphenylamine NDA is 10:1 to 1: 10;
step 3), adding the nano-silica composite filler component obtained in the step 1) into the mixed solution obtained in the step 2), wherein the nano-silica composite filler component accounts for 1.0-5.0 wt% of the total mass of the ODA and the NDA;
step 4) adding a dianhydride monomer PMDA in batches to the mixed solution obtained in step 3), and the amount of the added dianhydride monomer PMDA is equal to the sum of the amounts of the 4, 4 '-diaminodiphenyl ether ODA and the 4, 4' -diaminodiphenyl ether NDA, thereby obtaining a polyamic acid solution PAA;
and 5) coating the mixed solution obtained in the step 4) on a substrate, and heating the substrate at 100-400 ℃ for at least 5 hours to obtain the intrinsic black polyimide film.
In a further preferred embodiment, the long-chain organic auxiliary agent is selected from one of maleic acid ditridecyl ester, maleic acid ditetradecyl ester, or maleic acid dihexadecyl ester.
In an alternative embodiment of the present invention, the long-chain organic auxiliary is selected from dicetyl maleate, and the dicetyl maleate is prepared by the following steps:
using maleic anhydride and hexadecanol as raw materials, wherein the weight percentage of the raw materials is 1-5 parts of maleic anhydride: mixing 1 to 10 parts of hexadecanol, placing the mixture into an excessive solvent, adding p-toluenesulfonic acid accounting for 0.1 to 0.5 weight percent of the total mass of maleic anhydride and hexadecanol, continuously stirring and reacting at a temperature of between 80 and 160 ℃, and then obtaining the dicetyl maleate through the steps of neutralization, washing and drying.
In an alternative embodiment of the present invention, step 4) is performed according to the following operations: wherein the dianhydride monomer PMDA is added to the mixed solution obtained in the step 3) in 4 batches, one fourth of the total amount is added in each addition, and the mixed system is continuously stirred for at least 15 minutes after each addition.
In an alternative embodiment of the present invention, the heating in step 5) is performed at 100 ℃ to 400 ℃ for at least 5 hours, and the heating temperature and the heating time are sequentially performed as follows: heating at 60-100 deg.C for 1-3 hr; heating at 105-120 deg.C for 0.5-1 hr; heating at 150-200 deg.C for 1-2 hr, and heating at 220-260 deg.C for 1-2 hr; heating at 300 to 320 ℃ for 0.5 to 1 hour; heating at 380-420 deg.C for 0.5-1 hr.
In another aspect of the present invention, there is provided an intrinsic black polyimide film having improved mechanical properties, the intrinsic black polyimide film being obtained by any one of the methods described above.
Further, the intrinsic black polyimide film has a tensile strength of more than 150Mpa at normal temperature, has an elongation at break of more than 35%, and has a light transmittance of less than 0.5%.
According to the technical scheme provided by the invention, the improved mechanical property and the good breakdown-resistant electrical property of the polyimide film can be ensured while the high content of the intrinsic black NDA component is ensured.
The technical solutions and advantages of the present invention will be explained and explained in more detail below with reference to specific embodiments. It should be understood that the contents presented in the description and the detailed description are only for more clearly illustrating the technical solutions and the advantages of the present invention, and do not limit the protection scope of the present invention. On the basis of the disclosure of the specification, a person skilled in the art can modify the technical solution according to various reasonable changes, and the modified technical solution should be understood as being included in the protection scope of the invention as long as the person does not depart from the spirit of the invention.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosed embodiments and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the principles of the disclosure and not to limit the disclosure.
FIG. 1 is a schematic flow diagram of a process for preparing an intrinsically black polyimide film with improved mechanical properties according to the present invention;
FIG. 2 is an infrared spectrum of a polyimide film prepared in examples of the present invention and comparative examples;
FIG. 3 is a TEM image of polyimide films prepared in examples of the present invention and comparative examples.
Detailed Description
The present invention is described in more detail below to facilitate an understanding of the invention.
Before describing particular embodiments, it is to be understood that the sources of the starting materials described in the detailed description are not limiting, and that those skilled in the art will be able to select appropriate starting materials and testing equipment to perform the relevant tests and achieve the corresponding results in light of the teachings and teachings of the present invention, and that those skilled in the art will be able to select starting materials that meet the corresponding requirements from the disclosure and requirements of the present description for starting materials that do not describe a particular manufacturer or route. It will also be understood from the disclosure of the present specification that the reaction starting materials for the synthesis of a portion of the compounds are derived from the initial product synthesized in the preceding step of the present invention.
Part of raw material selection and sources:
the infrared test adopts a Nicolet iS50 FT-IR Fourier transform infrared spectrometer produced by ThermoFisher in America;
the transmission electron microscope test was performed using a Tecnai type TEM analyzer from FEI, USA;
the tensile strength test adopts an MST-I type tensile tester produced by Shimadzu corporation of Japan, and the experimental speed is 15mm/min;
the elongation at break adopts an MST-I type tension tester produced by Shimadzu corporation, and the experimental speed is 15mm/min;
the light transmission performance test adopts a UV756 type ultraviolet spectrophotometer of Shanghai Yokoku science and technology Limited company;
viscosity measurements were made using a DV2TRV viscometer from Bohler fly (Brookfield) USA, and the measured viscosity is expressed in terms of the intrinsic viscosity, which is a commonly used expression for the viscosity of polymer solutions. Units used are deciliters per gram (dL/g);
the breakdown strength test adopts a DDJ-100kv voltage breakdown tester produced by Beijing crown essence tester equipment Co.Ltd;
the nano-silica particles were purchased from Diagnano-box silica particles of Anbici organism (Abace Biotechnology). The grain diameter is about 30 nm;
bentonite for comparative experiments was purchased from Bentonite material of Beijing Atlanthoidecaological science and technology development Limited (CAS: 1302-78-9, Sigma-285234; particle size distribution: 500nm to 1.5 μm).
Preparation example 1: preparation of long-chain structure auxiliary agent
As previously mentioned, the long chain stracturant builder component of the invention may be selected from alkyl esters. In this preparation, a dicetyl maleate component was prepared. Selecting maleic anhydride and hexadecanol as raw materials, wherein the weight percentage of the raw materials is that the raw materials are 1 part of maleic anhydride: 5 parts of hexadecanol are mixed, the mixture is put into an excessive toluene solvent, p-toluenesulfonic acid accounting for 0.3wt% of the total mass of maleic anhydride and raw material alcohol is added, the mixture reacts for 3 hours under the condition of continuous stirring at 150 ℃, the solvent is removed through distillation, and the long-chain compound of the maleic acid dicetyl ester is obtained through neutralization, cleaning and drying.
Preparation example 2
And (3) preparing the nano silicon dioxide composite filler component. In this example, the nano-silica particles were purchased from Diagnano-silica particles of Anobique (Abace Biotechnology). To better achieve compatibility and miscibility with NDA molecules, a commercial product of about 30nm (D50) was selected in this example. In a preferred embodiment of the invention, the nanosilica particles preferably have a size of from 10nm to 50 nm.
Those skilled in the art know that even if the nano silica particles provided by the above specific suppliers are not purchased, those skilled in the art can synthesize and obtain nano silica particles having a specific particle size distribution. In a typical preparation method of nano silica particles, Tetraethoxysilane (TEOS) can be used as a raw material, and the reaction temperature, the reaction time and NH are adjusted 4OH、H2The concentration or proportion of O and TEOS is used to control the particle size and the particle size distribution of the silicon dioxide, and the silicon dioxide nano-particle product with uniform particle size distribution is obtained.
Next, in the present preparation example, 30nm nano silica particles and dicetyl maleate obtained in preparation example 1 were mixed in a ratio of the amount of substance of 1: 0.5, and fully stirring the mixture by using a stirring device at the speed of 300r/min to obtain the nano silicon dioxide composite filler component.
Example 1
This example will prepare an intrinsically black polyimide film with improved mechanical properties prepared from a dianhydride monomer (PMDA), 4 '-diaminodiphenyl ether (ODA), 4' -diaminodiphenylamine (NDA), and a nano-silica composite filler component. The flow chart of the method can be referred to fig. 1.
Referring to fig. 1, firstly, an excess amount of N, N-dimethylacetamide (acetyldimethylamine, DMAc) is added into a container to form a solvent, and 0.04mol of 4, 4' -diaminodiphenyl ether (ODA) is added under the conditions of nitrogen protection and ice-water bath, and the mixture is stirred for 15 minutes at a stirring speed of 150 r/min; then adding 0.06mol of 4, 4' -diaminodiphenylamine (NDA) and fully stirring for 15 minutes; after the ODA and the NDA were sufficiently mixed, the nano-silica composite filler component obtained in preparation example 2 was added in an amount of 2.5wt% based on the total mass of the ODA and the NDA, and stirred again at the same speed of 150r/min for 15 minutes.
Thereafter, dianhydride monomer (PMDA) was added in 4 portions, respectively, and stirring was continued under water cooling for 4 hours after 0.025mol was added each time, and stirring was further continued under water cooling for 2 hours after 0.1mol dianhydride monomer (PMDA) was added in total, thereby obtaining a polyamic acid solution (PAA).
Next, the prepared polyamic acid solution (PAA) was uniformly poured onto a glass plate, coated with a film using an automatic film coating machine, and then placed in a drying oven to prepare a polyimide film by temperature-programmed as follows: heating at 100 deg.C for 3h, 120 deg.C for 1h, 200 deg.C for 1h, 250 deg.C for 1h, 300 deg.C for 1h, and 400 deg.C for 1h to imidize the polyamic acid solution (PAA) to obtain polyimide. And (5) after the film is naturally cooled to room temperature, soaking the glass plate in distilled water until the film is completely peeled. The polyimide obtained was dried in an oven at 150 ℃ for 4h to remove any moisture that may be present.
Examples 2 to 5
Examples 2 to 5 similar preparation processes to example 1 were carried out except that different ratios of ODA and NDA were used in step 1 to mix well. NDA accounts for 0% to 80% of the total amount of both substances. Wherein the NDA in example 2 is 0, the NDA in example 3 is 20%, the NDA in example 4 is 40%, and the NDA in example 5 is 80%.
Examples 6 to 9
Examples 6 to 9 also carried out a similar preparation process to example 1, except that in step 1 different mass ratios of the nanosilica composite filler component were used. The nano silicon dioxide composite filler component accounts for 0.1wt% to 10wt% of the total mass of the ODA and the NDA. Wherein the nano-silica composite filler accounts for 0.1wt% of the total mass of the ODA and the NDA in the embodiment 6, 1wt% of the nano-silica composite filler in the embodiment 7, 5wt% of the nano-silica composite filler in the embodiment 8, and 10wt% of the nano-silica composite filler in the embodiment 9.
Comparative example 1
Comparative example 1 an intrinsically black polyimide film was prepared according to a similar procedure to that of example 1, except that the nano silica composite filler component described in preparation example 2 was not used in comparative example 1.
Comparative example 2
Comparative example 2 an intrinsic black polyimide film was prepared according to the similar procedure of example 1, but using a commercially available ultra-fine montmorillonite having a particle size distribution of 500nm to 1.5 μm from Beijing Atlanta Coptics Biotech development Co., Ltd, which is different from example 1 in terms of additives.
Test and results
The inventors made measurements on the examples and comparative examples, and the results are shown in table 1 below and specifically described.
First, infrared spectrum test (FT-IR) was performed on the polyimide films of example 1 and comparative example 1. See fig. 2 for test results. Example 1 is the lower infrared curve, comparative example 1 is the upper curve, and both example 1 and comparative example 1 are at 1720 cm –1And 1780 cm–1The occurrence of a distinct characteristic absorption peak of the imine ring proves that thermal imidization has occurred to give a polyimide body. About 720cm–1Characteristic peaks of the imide also appear, indicating that polyimide bodies were synthesized in both example 1 and comparative example 1. Except that, in example 1, about 3438 to 3440 cm-1Shows more peaks than comparative example 1, here corresponding to the absorption peak of Si — OH, indicating the presence of silicon oxide; 3048-1To 3057cm-1The overlapping peaks appearing close to each other belong to absorption peaks of cis-buten, indicating the presence of cis-buten type bonding substances.
On the basis of the synthesis of the polyimide film, the results of the respective synthesis examples were also characterized in terms of properties.
Table 1: preparation process of intrinsic black polyimide film
It can be seen from the above examples and comparative examples that the polyimide film with the composite silica filler of the present invention can ensure good mechanical properties, even improve mechanical properties, while ensuring good light shielding properties and acceptable breakdown properties, on the premise of adding a larger amount of NDA. The technical scheme of the invention can improve the mechanical property and ensure the synthesis of the intrinsic black polyimide. It is shown in examples 2 to 5 that the flowing viscosity of PAA can be effectively maintained even though the content of NDA is increased to be high, thereby synthesizing a polyimide film with high strength. It is also worth noting that the content of the nano silica composite filler should be reasonable to ensure the comprehensive performance of the polyimide film. Wherein when the proportion of the nano silica composite filler is less than 1wt%, it will be insufficient to improve the mechanical properties of the polyimide film (e.g., example 6), and when it exceeds 5wt%, the mechanical properties and PAA viscosity are also decreased, so that in the embodiment of the present invention, it is preferable that the nano silica composite filler accounts for 1wt% to 5wt% of the total mass of the ODA and the NDA. Preferably from 1wt% to 2.5 wt%.
The inventors have found, by comparison example 2, that the long chain structure aid component, and the matching of the filler to the NDA particle size, are important to the present invention. In the montmorillonite test, the deviation degree of the montmorillonite sample particles is relatively large, which may cause that the filler cannot achieve better compatibility with the NDA particles. Meanwhile, when no dicetyl maleate long-chain auxiliary exists, filler particles cannot be connected in series to form an ordered network, and the filler particles cannot be associated with micro nanoparticles of components with black pigment properties such as NDA and the like and silica auxiliary. The particle size distribution of the nanoparticulate silicas of the invention with long-chain alkyl maleates is therefore the preferred component.
The inventors have further tested embodiments of the invention to illustrate its structure and performance in order to better disclose and describe the features of the invention.
The inventors further performed Transmission Electron Microscopy (TEM) tests on the thin polyimide section layers of example 1 and comparative example 1. A) of fig. 3 is a thin layer slice TEM image of the polyimide film manufactured according to example 1 of the present invention. B) of fig. 3 is a TEM image of the thin layer of comparative example 1 according to the present invention. As can be seen from the a) compositional spectrum test in combination with the selective area electron diffraction of fig. 3, the composite filler (darker particles) component of silica is more uniformly mixed with the particles of diaminodiphenylamine (NDA) (lighter particles), and the lighter particles are represented as NDA particles and the darker particles are represented as silica particles due to the principle of TEM's light projection. Although the molecular structure of the long chain organic compound dicetyl maleate cannot be shown in TEM, comparing a) of fig. 3 with b) of fig. 3 shows that the NDA particles in the composite filler containing no silica in b) of fig. 3 and the additive of the long chain molecular structure of dicetyl maleate are distributed unevenly and the particles in part are agglomerated, which may cause the viscosity of the mixture raw material of the polyimide film to decrease after the proportion of NDA in the matrix increases, thereby deteriorating the mechanical strength. In the polyimide film provided by the technical scheme of the invention, the NDA and the silicon dioxide long-chain auxiliary agent components have good compatibility with each other, and the uniformly distributed network keeps good mechanical tensile and breaking properties of the film.
According to the embodiments and technical contents described in the present specification, the present invention can provide at least the following technical means: while the present disclosure includes specific embodiments, it will be apparent to those skilled in the art that various substitutions or alterations in form and detail may be made to these embodiments without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents. The embodiments described herein are to be considered in all respects only as illustrative and not restrictive. The description of features and aspects in each embodiment is believed to be applicable to similar features and aspects in other embodiments. Therefore, the scope of the present disclosure should be defined not by the detailed description but by the claims, and all changes within the scope of the claims and equivalents thereof should be construed as being included in the technical solution of the present disclosure.
Claims (7)
1. A method for preparing an intrinsically black polyimide film having improved mechanical properties, comprising the steps of: step 1), mixing nano silicon dioxide particles with a long-chain organic auxiliary agent to obtain a nano silicon dioxide composite filler component, wherein the mass ratio of the nano silicon dioxide particles to the long-chain organic auxiliary agent is 1:1 to 1: 0.1; a step 2) of mixing 4, 4 '-diaminodiphenyl ether ODA, 4' -diaminodiphenylamine NDA, and the nanosilica composite filler component, wherein the ratio of the amount of the substance of 4, 4 '-diaminodiphenyl ether ODA to the amount of the substance of 4, 4' -diaminodiphenylamine NDA is 10:1 to 1: 10; step 3), adding the nano-silica composite filler component obtained in the step 1) into the mixed solution obtained in the step 2), wherein the nano-silica composite filler component accounts for 1.0-5.0 wt% of the total mass of the ODA and the NDA; step 4) adding a dianhydride monomer PMDA in batches to the mixed solution obtained in step 3), and the amount of the added dianhydride monomer PMDA is equal to the sum of the amounts of the 4, 4 '-diaminodiphenyl ether ODA and the 4, 4' -diaminodiphenyl ether NDA, thereby obtaining a polyamic acid solution PAA; and 5) coating the mixed solution obtained in the step 4) on a substrate, and heating the substrate at 100-400 ℃ for at least 5 hours to obtain the intrinsic black polyimide film.
2. The method of claim 1, wherein the long-chain organic auxiliary agent is selected from one of bisdodecyl maleate, bistetradecyl maleate or dihexadecyl maleate.
3. The method of preparing an intrinsically black polyimide film with improved mechanical properties of claim 2, wherein the long-chain organic auxiliary agent is selected from dicetyl maleate, and the dicetyl maleate is prepared by the steps of: using maleic anhydride and hexadecanol as raw materials, wherein the weight percentage of the raw materials is 1-5 parts of maleic anhydride: mixing 1 to 10 parts of hexadecanol, placing the mixture into an excessive solvent, adding p-toluenesulfonic acid accounting for 0.1 to 0.5 weight percent of the total mass of maleic anhydride and hexadecanol, continuously stirring and reacting at a temperature of between 80 and 160 ℃, and then obtaining the dicetyl maleate through the steps of neutralization, washing and drying.
4. The method for preparing an intrinsically black polyimide film having improved mechanical properties of any one of claims 1 to 3, wherein the step 4) is performed as follows: wherein the dianhydride monomer PMDA is added to the mixed solution obtained in the step 3) in 4 batches, one fourth of the total amount is added in each addition, and the mixed system is continuously stirred for at least 15 minutes after each addition.
5. The method for preparing an intrinsically black polyimide film having improved mechanical properties as claimed in claim 1, wherein the heating at 100 ℃ to 400 ℃ in step 5) is performed for at least 5 hours at the following heating temperatures and heating times in order: heating at 60-100 deg.C for 1-3 hr; heating at 105-120 deg.C for 0.5-1 hr; heating at 150-200 deg.C for 1-2 hr, and heating at 220-260 deg.C for 1-2 hr; heating at 300 to 320 ℃ for 0.5 to 1 hour; heating at 380-420 deg.C for 0.5-1 hr.
6. An intrinsically black polyimide film having improved mechanical properties, which is prepared by the method of any one of claims 1 to 5.
7. The intrinsic black polyimide film with improved mechanical properties as claimed in claim 6, wherein the intrinsic black polyimide film has a tensile strength of more than 150Mpa at normal temperature, has an elongation at break of more than 35%, and has a light transmittance of less than 0.5%.
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| CN107216471A (en) * | 2017-08-02 | 2017-09-29 | 桂林电器科学研究院有限公司 | A kind of preparation method of multilayer black matt polyimide film |
| CN109180936A (en) * | 2018-09-28 | 2019-01-11 | 天津市天缘电工材料股份有限公司 | A kind of intrinsic black polyamide thin film and preparation method thereof and purposes |
| WO2019093669A2 (en) * | 2017-11-10 | 2019-05-16 | 에스케이씨코오롱피아이 주식회사 | Ultra-thin black polyimide film and manufacturing method therefor |
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2021
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216471A (en) * | 2017-08-02 | 2017-09-29 | 桂林电器科学研究院有限公司 | A kind of preparation method of multilayer black matt polyimide film |
| WO2019093669A2 (en) * | 2017-11-10 | 2019-05-16 | 에스케이씨코오롱피아이 주식회사 | Ultra-thin black polyimide film and manufacturing method therefor |
| CN109180936A (en) * | 2018-09-28 | 2019-01-11 | 天津市天缘电工材料股份有限公司 | A kind of intrinsic black polyamide thin film and preparation method thereof and purposes |
Non-Patent Citations (1)
| Title |
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| YAN ZHANG ET AL.,: "Molecular design, synthesis and characterization of intrinsically black polyimide films with high thermal stability and good electrical properties", 《JOURNAL OF POLYMER RESEARCH》 * |
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