CN109912618B - Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film - Google Patents
Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film Download PDFInfo
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Abstract
The invention discloses a multifunctional organic acid anhydride and a low-dielectric-constant hyperbranched polyimide film, wherein the low-dielectric-constant hyperbranched polyimide film is formed by polymerizing aromatic dicarboxylic anhydride, aromatic diamine and the multifunctional organic acid anhydride, the ratio of the mole number of total acid anhydride to the mole number of total amino groups is 1:1 in the polymerization process, and the used catalyst accounts for 0.1-2 mol% of the total mole amount of total acid anhydride and diamine monomers. The multifunctional organic acid anhydride monomer forms a hyperbranched structure in the PI molecular structure, so that the stacking density of PI molecules is effectively reduced, and the molar polarization density of PI is reduced. Compared with the PI film synthesized without adding the polyfunctional organic acid anhydride provided by the invention, the dielectric constant of the polyimide film prepared by the invention is reduced by 13.1-31.6%, the lowest dielectric constant is 2.4, and the application requirements in the technical fields of future high frequency, high speed and 5G communication can be effectively met.
Description
Technical Field
The invention relates to the field of polyimide resin films, in particular to novel multifunctional organic acid anhydride and a low-dielectric-constant hyperbranched polyimide film prepared from the same.
Background
With the rapid development of the scientific and technical and information era, high-frequency and high-speed communication is one of the major trends in the future. Currently, 4G communication is widely used, and 5G will gradually enter people's lives in the next 5-10 years. The 5G communication has higher speed information transmission capability, and the signal transmission speed is more than 10 times of that of the 4G communication. However, 5G communication puts higher demands on mobile communication devices, radio frequency base stations, integrated circuits and related electronic components. In the 5G era, integrated circuits in electronic products are developing towards high density, line width dimensions of various components and circuits are gradually reduced, signal transmission delay is caused by signal crosstalk and resistance-capacitance delay, and negative effects such as power dissipation are generated, so that the development of 5G communication is a significant obstacle. In high frequency and high speed communication, the transmission speed, delay, signal interference, power loss, etc. of signals are mainly determined by the dielectric constant (Dk) of the integrated circuit dielectric. The smaller the dielectric constant, the faster the signal transmission, the smaller the delay, and the lower the power consumption. Therefore, the development of a novel dielectric material with a low dielectric constant is one of the problems to be solved in the technical field of high-frequency and high-frequency 5G communication.
Polyimide (PI) is widely used in the fields of microelectronics and integrated circuits, particularly in portable electronic devices, because of its excellent mechanical and heat-resistant properties. The PI has good flexibility and can be used as a base material of future flexible display and flexible communication equipment. However, the intrinsic dielectric constant of PI is generally between 3.0-3.6, and the dielectric property can not meet the requirement of future high-frequency high-speed 5G communication technology (Dk < 2.8). In order to solve the problem, the scientific community has conducted intensive research on the low dielectric constant PI, and a plurality of stage results are obtained. According to the fundamental theory of dielectric constant, the main factors affecting the dielectric constant of a material are the molar polarizability of dielectric molecules and the polarizability density. The research work of scientific research is also mainly carried out in the two aspects. For example, introduction of fluorine atoms into PI can lower the dielectric constant based on a lower molar polarizability of C — F bonds (0.56). However, the method has a limited reduction of the dielectric constant, and the introduction of fluorine greatly increases the production cost of PI. Furthermore, the introduction of fluorine also leads to negative effects such as an increase in the PI coefficient of thermal expansion, poor adhesion and creep resistance. By introducing a porous structure into the PI, the density of polarized molecules per unit volume in the PI can be reduced, thereby efficiently reducing the dielectric constant of the PI. The dielectric constant of the prepared porous PI can be reduced to 2.0 or even lower, and the preparation method comprises a thermal decomposition method, a chemical etching method, a microphase separation method and the like. However, many research results show that the obtained low dielectric porous PI material tends to sacrifice the specific heat resistance and mechanical properties thereof. In addition, the porous preparation is often uneven and uncontrollable, and is difficult to scale up and implement industrial preparation and production, and cannot meet the future development requirements. Therefore, finding a simple, easily industrialized and cheap method for preparing PI with low dielectric constant, excellent heat resistance and mechanical properties is an important challenge for development of high-frequency and high-speed 5G communication in the future.
Disclosure of Invention
The invention aims to provide a multifunctional organic acid anhydride and a low-dielectric-constant hyperbranched polyimide film aiming at the defects of the prior art. The novel multifunctional organic acid anhydride can be used as a branching central site in PI, so that the intrinsic free volume of the PI is increased, and the stacking density of PI molecules is reduced, thereby effectively reducing the dielectric constant, and simultaneously keeping the excellent heat resistance and mechanical properties of the PI.
The purpose of the invention is realized by the following technical scheme: a polyfunctional organic acid anhydride, which has the following chemical structural formulae (1) to (3):
a hyperbranched polyimide film with low dielectric constant is prepared by the following steps:
(1) sequentially adding an organic solvent, aromatic diamine, aromatic dicarboxylic anhydride and polyfunctional organic anhydride into a reaction vessel, and reacting for 2-12h at 0-35 ℃ under the protection of nitrogen to obtain a polyamic acid precursor solution; in the reaction system, the molar ratio of the total amount of the aromatic dibasic acid anhydride and the polyfunctional organic acid anhydride to the aromatic diamine is 1: 1; the mol content of the polyfunctional organic acid anhydride in the total amount of the aromatic diamine, the aromatic dicarboxylic anhydride and the polyfunctional organic acid anhydride is 0.1-5%; and the total mass of the aromatic diamine, the aromatic dicarboxylic anhydride and the polyfunctional organic anhydride is 8-30 wt% of the polyamic acid precursor solution;
(2) adding a catalyst into the polyamic acid precursor solution obtained in the step (1), wherein the dosage of the catalyst is 0.1-2 mol% of the total molar weight of all acid anhydride and diamine used in the polyamic acid precursor solution, stirring the solution for 1-6h, then casting the polyamic acid precursor solution into a film at room temperature by using a casting machine, drying the film at 40-60 ℃, and reacting at 80-150 ℃ for 1-6h to obtain the hyperbranched polyimide film with low dielectric constant.
Further comprising the step of biaxially stretching the low dielectric constant hyperbranched polyimide film obtained in the step (2). The specific process of the biaxial stretching is as follows: the temperature is 100 ℃ and 250 ℃, the tensile strength is 10-50Mpa, and the tensile time is 5-60 min.
Further, the chemical structural formula of the aromatic dicarboxylic anhydride is shown in the following structural formulas (4) to (13):
further, the chemical structural formula of the aromatic diamine is shown in the following structural formulas (14) to (23):
further, the organic solvent is formed by mixing one or more of N-methyl pyrrolidone, N-dimethylformamide, p-cresol, o-cresol, m-cresol, N-dimethylacetamide, dimethyl sulfoxide and diethylene glycol monomethyl ether according to any proportion.
Furthermore, the catalyst is formed by mixing one or two of acetic anhydride or pyridine according to any proportion.
The invention has the beneficial effects that three novel multifunctional organic acid anhydride monomers are provided firstly and are used as branching sites to synthesize the hyperbranched polyimide film with low dielectric constant, good heat resistance and high tensile strength by a one-step method. Due to the introduction of a novel multifunctional organic acid anhydride monomer, a hyperbranched structure is formed in the PI molecular structure, the stacking density of PI molecules is effectively reduced, and the molar polarization density of PI is reduced. In addition, the three novel multifunctional organic acid anhydride monomers have larger intrinsic volume and are non-aromatic alicyclic structures, and the molar polarizability of the three novel multifunctional organic acid anhydride monomers is far lower than that of aromatic organic acid anhydrides, so that the dielectric constant of PI can be remarkably reduced. Because the content of the introduced multifunctional organic acid anhydride is controlled within a certain range, the influence on the inherent excellent heat resistance and mechanical property of the integral PI is small. Under the same test conditions, compared with a PI film synthesized without adding the multifunctional organic acid anhydride provided by the invention, the dielectric constant of the polyimide film prepared by the invention is reduced by 13.1-31.6%, the lowest dielectric constant is 2.4, and the application requirements in the future high-frequency high-speed and 5G communication technical fields can be effectively met.
Drawings
FIG. 1 is a chemical structure diagram of a hyperbranched polyimide film with low dielectric constant.
Detailed Description
In order to better understand the present invention, the following detailed description of the present invention is provided with specific examples, but the scope of the present invention is not limited to the scope shown in the examples, and the temperature, time and other process conditions in the preparation method can be selected according to the circumstances without substantially affecting the result.
Parameter measurement
Dielectric constant
The functionalized carbon quantum dot/polyimide composite membrane is dried in an oven at 105 ℃ for 24 hours in advance, the size of the polyimide membrane is 2 multiplied by 2cm, and the thickness is 25 mu m. The dielectric constant of the polyimide film is tested by an Agilent vector network analyzer N5230A and a resonator method, and the test frequency is 1MHz respectively.
Tensile strength
The mechanical property is tested by a universal material testing machine KSM-20KN, and the tensile strength of the parameter material is tested.
Thermal stability
The glass transition temperature (Tg) and the decomposition temperature (Tw) at 5 wt% weight loss were measured by TGA/DSC. The heating rate is 10 ℃/min, the maximum temperature is 800 ℃, and nitrogen is used for protection in the test process.
Example 1
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (9.7mmol) and the multifunctional organic anhydride A (0.1mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 ℃, the tensile strength is 40Mpa, the tensile time is 30min, and the chemical structure of the prepared hyperbranched polyimide film with low dielectric constant is shown in figure 1.
Example 2
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (9.4mmol) and the multifunctional organic anhydride A (0.2mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
Example 3
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (8.5mmol) and the multifunctional organic anhydride A (0.5mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
Example 4
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (9.7mmol) and the multifunctional organic anhydride B (0.1mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
Example 5
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (9.4mmol) and the multifunctional organic anhydride B (0.2mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
Example 6
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (8.5mmol) and the multifunctional organic anhydride B (0.5mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
Example 7
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (9.6mmol) and the multifunctional organic anhydride C (0.1mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
Example 8
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (9.2mmol) and the multifunctional organic anhydride C (0.2mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
Example 9
Adding 30mL of N, N-dimethylacetamide, ODA (10mmol), a-BPDA (8.8mmol) and the multifunctional organic anhydride C (0.3mmol) in sequence into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
Comparative examples
Sequentially adding 30mL of N, N-dimethylacetamide, ODA (10mmol) and a-BPDA (10mmol) into a reaction vessel, and reacting at 25 ℃ for 10 hours under the protection of nitrogen to obtain a polyamic acid precursor solution; adding pyridine (0.15mmol) into the polyamic acid precursor solution, stirring the solution for 6h, casting the polyamic acid soluble precursor into a film at room temperature by using a casting machine, drying the film at 50 ℃, reacting the film for 4h at 100 ℃ to obtain a hyperbranched polyimide film with a low dielectric constant, and stripping the polyimide film from a casting belt by using stripping equipment. After the polyimide film is peeled off, a biaxial stretching process is further performed to increase the in-plane orientation of the polyimide. The stretching process comprises the following steps: the temperature is 150 deg.C, the tensile strength is 40Mpa, and the tensile time is 30 min.
The film samples obtained according to examples 1 to 9 and comparative examples were subjected to the performance parameter tests including dielectric constant Dk, tensile strength, and thermal stability, and the test results are shown in Table 1.
Table 1: properties of film samples obtained in different examples
| Sample (I) | Dk | Tensile strength/MPa | Tg/℃ | Tw/℃ |
| Example 1 | 3.05 | 110.6 | 392 | 571 |
| Example 2 | 2.76 | 105.2 | 387 | 568 |
| Example 3 | 2.62 | 98.3 | 381 | 565 |
| Example 4 | 3.01 | 104.7 | 389 | 572 |
| Example 5 | 2.82 | 101.2 | 384 | 569 |
| Example 6 | 2.65 | 97.8 | 381 | 567 |
| Example 7 | 2.87 | 100.9 | 388 | 565 |
| Example 8 | 2.54 | 96.2 | 384 | 562 |
| Example 9 | 2.40 | 94.5 | 379 | 554 |
| Comparative examples | 3.51 | 115.2 | 394 | 573 |
As shown in table 1, it can be seen from the results of the above examples that the hyperbranched polyimide thin hybrid film prepared by the present invention has low dielectric constant, high thermal stability and mechanical properties, and can meet the application requirements of future high-frequency high-speed 5G communication and related microelectronic industries.
Claims (7)
1. A polyfunctional organic acid anhydride, characterized in that it has the following chemical structural formula (1) to (2):
the multifunctional organic acid anhydride is used for preparing the hyperbranched polyimide film with low dielectric constant.
2. A low dielectric constant hyperbranched polyimide film based on the polyfunctional organic acid anhydride of claim 1, which is prepared by the following method:
(1) sequentially adding an organic solvent, aromatic diamine, aromatic dicarboxylic anhydride and polyfunctional organic anhydride into a reaction vessel, and reacting for 2-12h at 0-35 ℃ under the protection of nitrogen to obtain a polyamic acid precursor solution; in the reaction system, the molar ratio of the total amount of the aromatic dibasic acid anhydride and the polyfunctional organic acid anhydride to the aromatic diamine is 1: 1; the mol content of the polyfunctional organic acid anhydride in the total amount of the aromatic diamine, the aromatic dicarboxylic anhydride and the polyfunctional organic acid anhydride is 0.1-5%; and the total mass of the aromatic diamine, the aromatic dicarboxylic anhydride and the polyfunctional organic anhydride is 8-30 wt% of the polyamic acid precursor solution;
(2) adding a catalyst into the polyamic acid precursor solution obtained in the step (1), wherein the dosage of the catalyst is 0.1-2 mol% of the total molar weight of all acid anhydride and diamine used in the polyamic acid precursor solution, stirring the solution for 1-6h, then casting the polyamic acid precursor solution into a film at room temperature by using a casting machine, drying the film at 40-60 ℃, and reacting at 80-150 ℃ for 1-6h to obtain the hyperbranched polyimide film with low dielectric constant.
3. The low dielectric constant hyperbranched polyimide film according to claim 2, further comprising a step of biaxially stretching the low dielectric constant hyperbranched polyimide film obtained in the step (2); the specific process of the biaxial stretching is as follows: the temperature is 100 ℃ and 250 ℃, the tensile strength is 10-50Mpa, and the tensile time is 5-60 min.
4. The low-dielectric-constant hyperbranched polyimide film as claimed in claim 2, wherein the chemical structural formula of the aromatic dicarboxylic anhydride is as shown in the following structural formulas (4) to (13):
5. the low-dielectric-constant hyperbranched polyimide film as claimed in claim 2, wherein the chemical structural formula of the aromatic diamine is as shown in the following structural formulas (14) to (23):
6. the low-dielectric-constant hyperbranched polyimide film as claimed in claim 2, wherein the organic solvent is composed of one or more of N-methylpyrrolidone, N-dimethylformamide, p-cresol, o-cresol, m-cresol, N-dimethylacetamide, dimethyl sulfoxide, and diethylene glycol monomethyl ether, which are mixed in any ratio.
7. The low-dielectric-constant hyperbranched polyimide film as claimed in claim 2, wherein the catalyst is one or two of acetic anhydride and pyridine mixed according to any ratio.
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| CN102201595A (en) * | 2010-03-26 | 2011-09-28 | 三洋电机株式会社 | Lithium secondary battery and method for manufacturing the same |
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