CN115724815B - Dianhydride monomer containing amide structure and trifluoromethyl, polyimide film and preparation method thereof - Google Patents
Dianhydride monomer containing amide structure and trifluoromethyl, polyimide film and preparation method thereof Download PDFInfo
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- CN115724815B CN115724815B CN202211457487.7A CN202211457487A CN115724815B CN 115724815 B CN115724815 B CN 115724815B CN 202211457487 A CN202211457487 A CN 202211457487A CN 115724815 B CN115724815 B CN 115724815B
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000178 monomer Substances 0.000 title claims abstract description 55
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 title claims abstract description 31
- 229920001721 polyimide Polymers 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 125000003368 amide group Chemical group 0.000 title abstract 3
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 150000001408 amides Chemical group 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- KZSXRDLXTFEHJM-UHFFFAOYSA-N 5-(trifluoromethyl)benzene-1,3-diamine Chemical compound NC1=CC(N)=CC(C(F)(F)F)=C1 KZSXRDLXTFEHJM-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000006467 substitution reaction Methods 0.000 claims description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 claims description 3
- FJVIHKKXPLPDSV-UHFFFAOYSA-N 4-phenoxybenzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1OC1=CC=CC=C1 FJVIHKKXPLPDSV-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical compound CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 2
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims description 2
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 claims description 2
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- LOCTYHIHNCOYJZ-UHFFFAOYSA-N (4-aminophenyl) 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(N)C=C1 LOCTYHIHNCOYJZ-UHFFFAOYSA-N 0.000 claims 1
- 239000003989 dielectric material Substances 0.000 abstract description 7
- 239000011229 interlayer Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
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- 230000000052 comparative effect Effects 0.000 description 2
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- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ALYNCZNDIQEVRV-UHFFFAOYSA-M 4-aminobenzoate Chemical compound NC1=CC=C(C([O-])=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 238000012512 characterization method Methods 0.000 description 1
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- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
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- -1 on one hand Chemical group 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a dianhydride monomer containing an amide structure and trifluoromethyl, which has a structural formula shown in a formula (1). The invention also discloses a low dielectric constant polyimide film and a preparation method thereof, wherein the polyimide film is obtained by imidizing a polyamic acid solution, and dianhydride monomers in the raw materials of the polyamic acid solution comprise the dianhydride monomers containing an amide structure and trifluoromethyl. The dianhydride monomer is applied to the preparation of polyimide films, and can reduce the energy consumption loss of interlayer dielectrics in an integrated circuit (10 GHz) at high frequency, thereby greatly reducing the resistance-capacitance (RC) delay, crosstalk and power consumption in the integrated circuit, and simultaneously having excellent mechanical property and thermal stability and performance stability in the operation process.
Description
Technical Field
The invention relates to the technical field of polyimide materials, in particular to a dianhydride monomer containing an amide structure and trifluoromethyl, a polyimide film and a preparation method thereof.
Background
A package is a structure that interconnects semiconductor chips with each other and with peripheral devices such as input and output devices. Basically, the package can support subsequent processing, handling, and performance of the chip, can protect the chip from moisture, dust, and gases, and maintains the integrity of electrical signals to and from the chip. With the rapid development of integrated circuits, higher level integration (e.g., very large scale integrated circuits (VLSI), very High Speed Integrated Circuits (VHSIC), etc.) is occurring, thereby placing higher demands on circuit packaging. Thus, there is a need to achieve the desired functionality with minimal adverse impact on the performance, efficiency and lifetime of the packaged electronic circuit, where the dielectric properties of the packaging material play a critical role in the transmission of signals.
Dielectric properties include dielectric constants and dielectric losses, where dielectric constants are commonly used to describe dielectric properties of materials. The lower the dielectric constant and dielectric loss, the less energy is absorbed from the electric field. In microelectronic packages, low dielectric materials are required, low dielectric constants (2.0 to 3.0) should remain almost unchanged over a wide frequency range from direct current to GHz, and dielectric losses should be frequency independent. PI meets such dielectric requirements and is widely used in interlayer dielectrics in integrated circuits with its stable thermal properties, good mechanical properties and dielectric properties to counteract package delays caused by signal-dielectric interactions.
The use of low-k interlayer dielectrics can greatly reduce resistance-capacitance (RC) skew, cross-talk, and power consumption in new generation high-density high-speed integrated circuits. Therefore, there has been great interest in PI films for use in interlayer dielectrics in integrated circuits in recent years. In addition to the need for low dielectric constants, PI films as interlayer dielectrics for integrated circuits are also required to have excellent mechanical and thermal properties, as well as performance stability during operation, in order to better accommodate the use requirements in the integrated circuit arts.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a dianhydride monomer containing an amide structure and trifluoromethyl, a polyimide film and a preparation method thereof, and aims to reduce energy consumption loss of interlayer dielectrics in an integrated circuit at high frequency (10 GHz), so that resistance-capacitance (RC) delay, crosstalk and power consumption in the integrated circuit can be greatly reduced, and simultaneously, the dianhydride monomer containing the amide structure and the trifluoromethyl has excellent mechanical property and thermal stability and performance stability in the operation process.
The structural formula of the dianhydride monomer containing the amide structure and the trifluoromethyl is shown as the formula (1):
A method for preparing the dianhydride monomer containing an amide structure and trifluoromethyl, which comprises the following steps: in a solvent, 3, 5-diamino benzotrifluoride and 1,2, 4-trimellitic anhydride acyl chloride are subjected to substitution reaction in an inert atmosphere in the presence of an acid binding agent, and the catalyst is obtained.
Preferably, the molar ratio of 3, 5-diaminobenzotrifluoride to 1,2, 4-trimellitic anhydride acid chloride is 1:2-1:2.5.
Preferably, the acid binding agent is at least one of triethylamine, diisopropylethylamine, pyridine and 4-dimethylaminopyridine, and the solvent is at least one of dichloromethane, chloroform, N-dimethylformamide and N, N-dimethylacetamide.
Preferably, the temperature of the substitution reaction is 0-25 ℃ and the time is 6-12 h.
In the invention, the synthesis route of dianhydride monomer containing amide structure and trifluoromethyl is as follows:
The polyimide film with low dielectric constant is obtained by imidizing polyamide acid solution, wherein the polyamide acid solution is obtained by polycondensing diamine monomer and dianhydride monomer in a strong-polarity aprotic organic solvent;
preferably, the molar ratio of diamine monomer to dianhydride monomer is 1:1.
The dianhydride monomer comprises dianhydride A and dianhydride B, wherein the dianhydride A is the dianhydride monomer containing an amide structure and trifluoromethyl, the dianhydride B is at least one of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride and 4, 4-hexafluoroisopropyl phthalic anhydride, and the dianhydride A accounts for 20-60% of the total mole of the dianhydride monomers.
Preferably, the diamine monomer is at least one of p-phenylenediamine, m-phenylenediamine, 3, 4-diaminodiphenyl ether, 4-diaminodiphenyl methane, m-tolidine, 2' -bis (trifluoromethyl) diaminobiphenyl, 4' -diaminobenzidine, p-aminobenzoate, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ], 3, 5-diaminobenzotrifluoride.
Preferably, the strong polar aprotic organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
The preparation method of the low dielectric constant polyimide film comprises the following steps:
s1, under inert atmosphere, dissolving diamine monomer in a strong polar aprotic organic solvent, and then adding dianhydride monomer to stir and react to obtain polyamic acid solution;
S2, coating the polyamide acid solution on a substrate after defoaming, and sequentially performing prebaking and high-temperature imidization to obtain the low-dielectric-constant polyimide film.
Preferably, in S1, the viscosity of the polyamic acid solution is 20 to 100pa·s.
Preferably, in S2, the temperature is gradually increased from 80-110 ℃ to 300-310 ℃ for high Wen Ya amination.
A low dielectric constant polyimide film is prepared by the preparation method.
The beneficial effects of the invention are as follows:
The invention prepares a dianhydride monomer containing an amide structure and trifluoromethyl, and provides a low dielectric constant polyimide film prepared by adopting the dianhydride monomer containing the amide structure and trifluoromethyl, on one hand, fluorine atoms with larger polarity can be introduced into the film, the dianhydride monomer has stronger free electron binding capacity, and the molar polarizability of the film material can be effectively reduced; on the other hand, the novel dianhydride monomer also has larger volume steric hindrance, and correspondingly increases the free volume of a polymer molecular chain, so that the purposes of reducing the dielectric constant and dielectric loss of the film can be realized through the reduction of the molar polarizability and the increase of the molar volume, thereby greatly reducing the resistance-capacitance (RC) delay, crosstalk and power consumption in an integrated circuit. In addition, the amide structure in the monomer can improve the probability of forming hydrogen bonds of molecular chains and enhance the interaction between the molecular chains, thereby improving the mechanical property and the thermal stability of the film.
Drawings
FIG. 1 is a nuclear magnetic pattern of dianhydride monomer containing an amide structure and trifluoromethyl group prepared according to the present invention.
Detailed Description
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
Example 1
Preparing dianhydride monomer containing an amide structure and trifluoromethyl:
1.761g of 3, 5-diaminobenzotrifluoride was added to a round-bottom flask and nitrogen-protected, then 20mL of methylene chloride and 3mL of triethylamine were added, and stirred at room temperature under nitrogen atmosphere for 10min; dissolving 4.212g of 1,2, 4-trimellitic anhydride acyl chloride in 15mL of dichloromethane, adding the dichloromethane into a constant pressure dropping funnel, then dropwise adding the dichloromethane into a round bottom flask, adjusting the molar ratio of 3, 5-diaminobenzotrifluoride to 1,2, 4-trimellitic anhydride acyl chloride to be 1:2, and stirring the mixture at room temperature for reaction for 12 hours; after the reaction, the solution was distilled under reduced pressure to a solid, and the dianhydride monomer product was obtained after column chromatography separation, which was weighed to give 4.437g, with a yield of 85%.
The dianhydride monomer product containing the amide structure and trifluoromethyl is subjected to structural characterization, and the nuclear magnetic spectrum is shown in figure 1. Nuclear magnetic hydrogen spectrum 1H NMR (400 MHz, DMSO-d 6) chemical shift delta of dianhydride monomer containing amide structure and trifluoromethyl, 10.35-10.18 (c, 2H), 8.62-8.35 (e, f 4H), 8.07-7.89 (d, 2H), 7.85-7.7.68 (b, 3H), 7.62-7.46 (a, 4H).
Example 2
Preparing a low dielectric constant polyimide film:
S1, dissolving 4.283g of 4,4'- [1, 4-phenyl-bis (oxy) ] bis [3- (trifluoromethyl) aniline ], 2.273g of 4,4' -diaminoanilide and 1.000g of 3, 4-diaminodiphenyl ether in 21mL of N, N-dimethylacetamide, and stirring at room temperature under nitrogen atmosphere for 30min; then adding 4.362g of pyromellitic dianhydride and 2.612g of dianhydride monomer containing an amide structure and trifluoromethyl prepared in example 1 into a reaction kettle for multiple times, and stirring and reacting for 12 hours to obtain a polyamic acid solution with the viscosity of 50 Pa.s;
S2, placing the polyamic acid solution in a vacuum drying oven for defoaming for 2 hours, coating the polyamic acid solution on a dry and clean glass plate by using a coating machine, placing the glass plate in a blast drying oven, pre-drying the glass plate at 80 ℃ for 30 minutes, removing the film, transferring the film onto a needle frame, sending the film back into the blast drying oven for high-temperature imidization (sequentially heating to 110 ℃ for 30 minutes, 160 ℃ for 30 minutes, 210 ℃ for 30 minutes, 260 ℃ for 30 minutes and 310 ℃ for 30 minutes, and naturally cooling to room temperature after the high-temperature imidization is finished, thereby obtaining the polyimide film with low dielectric constant.
According to GB/T13542.2-2009 test standard, the polyimide film is subjected to mechanical and dielectric property test, and the result shows that: the low dielectric polyimide film prepared by the method has the thickness of 33+/-5 mu m, the tensile strength of 135MPa, the elongation at break of 19%, the tensile modulus of 4.0GPa, the dielectric constant of 2.6 and the dielectric loss of 0.006.
Example 3
The procedure of S1 was repeated except that "4.362 g of pyromellitic dianhydride and 2.612g of the dianhydride monomer containing an amide structure and trifluoromethyl group obtained in example 1 were added to the reaction vessel in multiple portions" replaced with "3.817 g of pyromellitic dianhydride and 3.918g of the dianhydride monomer containing an amide structure and trifluoromethyl group obtained in example 1 were added to the reaction vessel in multiple portions". The remainder was the same as in example 2.
The thickness of the low dielectric polyimide film prepared by the method is 33+/-5 mu m, the tensile strength is 146MPa, the elongation at break is 22%, the tensile modulus is 4.2GPa, the dielectric constant is 2.5, and the dielectric loss is 0.005.
Example 4
The procedure of S1 was repeated except that "4.362 g of pyromellitic dianhydride and 2.612g of the dianhydride monomer containing an amide structure and trifluoromethyl group obtained in example 1 were added to the reaction vessel in multiple portions" replaced with "3.272 g of pyromellitic dianhydride and 5.224g of the dianhydride monomer containing an amide structure and trifluoromethyl group obtained in example 1 were added to the reaction vessel in multiple portions". The remainder was the same as in example 2.
The thickness of the low dielectric polyimide film prepared by the method is 33+/-5 mu m, the tensile strength is 162MPa, the elongation at break is 27%, the tensile modulus is 4.5GPa, the dielectric constant is 2.2, and the dielectric loss is 0.003.
Comparative example 1
The "4.362 g of pyromellitic dianhydride and 2.612g of the dianhydride monomer containing an amide structure and trifluoromethyl group obtained in example 1 were added to the reaction vessel in multiple portions" in S1 was replaced by "5.453 g of pyromellitic dianhydride was added to the reaction vessel in multiple portions". The remainder was the same as in example 2.
The polyimide film prepared by the method has the thickness of 33+/-5 mu m, the tensile strength of 116MPa, the elongation at break of 15 percent, the tensile modulus of 3.7GPa, the dielectric constant of 2.8 and the dielectric loss of 0.009.
As can be seen from the comparison of the data of examples 2-4 and comparative example 1, the addition of the dianhydride monomer containing an amide structure and a trifluoromethyl group can effectively improve the tensile strength and tensile modulus of the film, and the fracture growth rate of the film is also improved, which indicates that the synthesized dianhydride monomer containing an amide structure and a trifluoromethyl group effectively enhances the mechanical properties of the film; the dielectric constant and dielectric loss of the film also decrease along with the increase of the dianhydride monomer, so that the dianhydride monomer can improve the mechanical property of the film material and simultaneously reduce the dielectric constant and dielectric loss of the film material.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. A dianhydride monomer containing an amide structure and trifluoromethyl is characterized in that the structural formula is shown as formula (1):
。
2. A process for the preparation of dianhydride monomer containing an amide structure and trifluoromethyl group as claimed in claim 1, which comprises: in a solvent, 3, 5-diamino benzotrifluoride and 1,2, 4-trimellitic anhydride acyl chloride are subjected to substitution reaction in an inert atmosphere in the presence of an acid binding agent, and the catalyst is obtained.
3. The method for producing a dianhydride monomer containing an amide structure and a trifluoromethyl group according to claim 2, wherein the molar ratio of 3, 5-diaminobenzotrifluoride to 1,2, 4-trimellitic anhydride acid chloride is 1:2 to 1:2.5.
4. The method for producing a dianhydride monomer containing an amide structure and a trifluoromethyl group according to claim 2, wherein the acid-binding agent is at least one of triethylamine, diisopropylethylamine, pyridine and 4-dimethylaminopyridine, and the solvent is at least one of dichloromethane, chloroform, N-dimethylformamide and N, N-dimethylacetamide.
5. The method for producing a dianhydride monomer containing an amide structure and a trifluoromethyl group as claimed in claim 2, wherein the temperature of the substitution reaction is 0 to 25 ℃ for 6 to 12 hours.
6. The polyimide film with low dielectric constant is characterized in that the polyimide film is obtained by imidizing a polyamic acid solution, wherein the polyamic acid solution is obtained by condensing diamine monomers and dianhydride monomers in a strong-polarity aprotic organic solvent;
The dianhydride monomer comprises dianhydride A and dianhydride B, wherein the dianhydride A is the dianhydride monomer containing an amide structure and trifluoromethyl, the dianhydride B is at least one of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride and 4, 4-hexafluoroisopropyl phthalic anhydride, and the dianhydride A accounts for 20-60% of the total mole of the dianhydride monomers.
7. The low dielectric constant polyimide film according to claim 6, wherein the diamine monomer is at least one of p-phenylenediamine, m-phenylenediamine, 3, 4-diaminodiphenyl ether, 4-diaminodiphenyl methane, m-tolidine, 2' -bis (trifluoromethyl) diaminobiphenyl, 4' -diaminobenzidine, p-aminophenyl p-aminobenzoate, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4' - [1, 4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ], 3, 5-diaminobenzotrifluoride; the strong polar aprotic organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
8. A method for producing the low dielectric constant polyimide film according to claim 6 or 7, comprising the steps of:
s1, under inert atmosphere, dissolving diamine monomer in a strong polar aprotic organic solvent, and then adding dianhydride monomer to stir and react to obtain polyamic acid solution;
S2, coating the polyamide acid solution on a substrate after defoaming, and sequentially performing prebaking and high-temperature imidization to obtain the low-dielectric-constant polyimide film.
9. The method for producing a low dielectric constant polyimide film according to claim 8, wherein in S1, the viscosity of the polyamic acid solution is 20 to 100pa·s;
in S2, the temperature is gradually increased from 80 to 110 ℃ to 300 to 310 ℃ for high Wen Ya amination.
10. A low dielectric constant polyimide film produced by the production method according to claim 8 or 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211457487.7A CN115724815B (en) | 2022-11-21 | 2022-11-21 | Dianhydride monomer containing amide structure and trifluoromethyl, polyimide film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211457487.7A CN115724815B (en) | 2022-11-21 | 2022-11-21 | Dianhydride monomer containing amide structure and trifluoromethyl, polyimide film and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN115724815A CN115724815A (en) | 2023-03-03 |
| CN115724815B true CN115724815B (en) | 2024-05-17 |
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Citations (4)
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| 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 |
| CN106170333A (en) * | 2013-12-02 | 2016-11-30 | 陶氏环球技术有限责任公司 | Composite polyamide membrane treated with dihydroxyaryl compound and nitrous acid |
| JP2019191370A (en) * | 2018-04-25 | 2019-10-31 | 東洋インキＳｃホールディングス株式会社 | Colored composition for color filter and color filter |
| CN112194790A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | Low-thermal-expansion transparent polyimide film and preparation method thereof |
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Patent Citations (4)
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| CN106170333A (en) * | 2013-12-02 | 2016-11-30 | 陶氏环球技术有限责任公司 | Composite polyamide membrane treated with dihydroxyaryl compound and nitrous acid |
| 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 |
| JP2019191370A (en) * | 2018-04-25 | 2019-10-31 | 東洋インキＳｃホールディングス株式会社 | Colored composition for color filter and color filter |
| CN112194790A (en) * | 2020-06-16 | 2021-01-08 | 中国科学院长春应用化学研究所 | Low-thermal-expansion transparent polyimide film and preparation method thereof |
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