CN115850699A - Low-dielectric blended polyimide, preparation method and application thereof - Google Patents
Low-dielectric blended polyimide, preparation method and application thereof Download PDFInfo
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- CN115850699A CN115850699A CN202211079828.1A CN202211079828A CN115850699A CN 115850699 A CN115850699 A CN 115850699A CN 202211079828 A CN202211079828 A CN 202211079828A CN 115850699 A CN115850699 A CN 115850699A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 76
- 239000004642 Polyimide Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- 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 claims abstract description 17
- 150000004985 diamines Chemical class 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 11
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical group C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003292 glue Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000003880 polar aprotic solvent Substances 0.000 claims description 10
- 239000011521 glass Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000004952 Polyamide Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 238000004377 microelectronic Methods 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004427 diamine group Chemical group 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- -1 bis (4-aminophenyl) thianthrene-2,7-dicarboxylate Chemical compound 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000013335 mesoporous material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- AYUWKNJMCFUOFF-UHFFFAOYSA-N thianthrene-2,7-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C2SC3=CC(C(=O)Cl)=CC=C3SC2=C1 AYUWKNJMCFUOFF-UHFFFAOYSA-N 0.000 description 3
- VIUDTWATMPPKEL-UHFFFAOYSA-N 3-(trifluoromethyl)aniline Chemical compound NC1=CC=CC(C(F)(F)F)=C1 VIUDTWATMPPKEL-UHFFFAOYSA-N 0.000 description 2
- RHLWTWUMSPIQMC-UHFFFAOYSA-N 9,9-bis(trifluoromethyl)xanthene-2,3,6,7-tetracarboxylic acid Chemical compound O1C2=CC(C(O)=O)=C(C(O)=O)C=C2C(C(F)(F)F)(C(F)(F)F)C2=C1C=C(C(=O)O)C(C(O)=O)=C2 RHLWTWUMSPIQMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- GUEMADKCYDBBFM-UHFFFAOYSA-N thianthrene-2,7-dicarboxylic acid Chemical compound OC(=O)C1=CC=C2SC3=CC(C(=O)O)=CC=C3SC2=C1 GUEMADKCYDBBFM-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
The invention discloses a preparation method of low dielectric blended polyimide, which is characterized in that diamine containing a thianthrene structure and ester bonds and fluorine-containing diamine are respectively blended with polyamic acid prepared from fluorine-containing dianhydride monomers, good affinity of thioether bonds and metal is utilized to improve the cohesiveness of polyimide and metal copper, and meanwhile, a rigid and planar structure is introduced to improve the thermal stability of polyimide and reduce the thermal expansion coefficient of the polyimide, and the intermolecular force of the polyimide can be enhanced by combining the ester bonds, so that the thermal expansion coefficient of the polyimide is reduced. The blended polyimide prepared by polymerizing and blending the three monomers has low dielectric constant, low thermal expansion coefficient and high thermal stability, and solves the problems of high and unstable dielectric constant, high thermal expansion coefficient and the like of the polyimide under low frequency.
Description
Technical Field
The invention relates to the technical field of polyimide materials, in particular to low dielectric blended polyimide, a preparation method and application thereof.
Background
With the rapid development of the fields of 5G, the Internet of things and the like, the microelectronic technology as a key technology in the fields has become a hot spot of world high-tech competition, but the requirements on the material performance are higher and higher. Polyimide is used as a key material applied in the field of microelectronics at present, and the dielectric constant is usually between 3.0 and 3.6, but in the face of the current requirements of high-frequency and high-speed signal transmission, the traditional polyimide material has difficulty in meeting the current requirements on dielectric materials, and gradually becomes a bottleneck limiting the development of microelectronic technology.
At present, in CN202111081267.4, a low dielectric polyimide-based composite film, a preparation method and an application thereof disclose that pyromellitic dianhydride and 4,4' -diaminodiphenyl are used as raw materials to prepare a polyamic acid solution, and then nano cage-type phenyl silsesquioxane is added to the polyamic acid solution to prepare the low dielectric polyimide-based composite film through imidization. According to the patent, nanometer holes are formed by introducing cage type phenyl silsesquioxane with a micropore structure into polyimide, and air (the dielectric constant is about 1.0) is introduced into a polyimide matrix to effectively reduce the dielectric constant of the polyimide. Although the addition of the mesoporous material to the polyimide can effectively reduce the dielectric constant, the method is greatly limited by the influence of the performance of the mesoporous material and the influence of the dispersion of the mesoporous material in the polyimide.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of low dielectric blended polyimide aiming at the defects of high and unstable dielectric constant of polyimide under low frequency in the prior art.
The invention provides a low dielectric blended polyimide and application thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of low dielectric blended polyimide comprises the following preparation steps:
s1, adding fluorine-containing diamine and fluorine-containing dianhydride into a polar aprotic solvent protected by inert gas in proportion, and stirring for reaction to obtain a homogeneous and viscous polyamide acid glue solution A;
s2, adding diamine containing a thianthrene structure and an ester bond and fluorine-containing dianhydride into a polar aprotic solvent protected by inert gas in proportion, and stirring for reaction to obtain a homogeneous and viscous polyamide acid glue solution B;
s3, mixing the polyamic acid glue solution A in the step S1 and the polyamic acid glue solution B in the step S2 together in proportion, controlling the temperature to be minus 10-40 ℃, and stirring for 4-12 hours to prepare a blending type polyamic acid glue solution;
and S4, uniformly coating the mixed polyamic acid glue solution obtained in the step S3 on clean glass, and imidizing the polyamic acid glue solution to obtain the polyimide film.
Further, the fluorine-containing diamine in step S1 is one or more of the following structures:
further, the diamine structure containing a thianthrene structure and an ester bond described in step S2 is:
further, the fluorine-containing dianhydride monomer is one or more of the following structures:
further, the molar ratio of the fluorine-containing diamine monomer to the dianhydride monomer in step S1 is 1.
Further, the strong polar aprotic organic solvent in steps S1 and S2 is one or more of N-methylpyrrolidone, dimethyl sulfoxide, dimethyl sulfone, sulfolane, 1,4-dioxane, N-dimethylacetamide, N-dimethylformamide, m-cresol, and tetrahydrofuran.
Further, the mass ratio of the polyamic acid solution a to the polyamic acid solution B in step S3 is 50 to 99.
Further, the mass fraction of the total mass of the diamine and the dianhydride in the steps S1 and S2 in the total mass of the reaction materials is 2-50%.
Furthermore, the stirring reaction time in the step S1 is 0.5-72 h, and the stirring reaction time in the step S2 is 0.5-72 h.
Further, the imidization in step S4 includes thermal imidization or chemical imidization.
Further, the gradient of the thermal imidization temperature rise is controlled as follows: the temperature is raised to 100 ℃ from room temperature and then kept constant for 0.8 to 3 hours, the temperature is raised to 200 ℃ from 100 ℃ and then kept constant for 0.8 to 2 hours, the temperature is raised to 300 ℃ from 200 ℃ and then kept constant for 0.8 to 2 hours, and the temperature is raised to 350 ℃ to 500 ℃ from 300 ℃ and then kept constant for 0.5 to 2 hours.
The polyimide prepared by the preparation method of the low dielectric blended polyimide is applied to the field of microelectronics.
Compared with the prior art, the beneficial effects are:
the method adopts homopolymerization for polymerization, has simple process and low cost, is more stable than copolymerization methods in reaction, forms polyamic acid A by polymerization of fluorine-containing diamine and fluorine-containing dianhydride, forms polyamic acid B by polymerization of diamine containing a thianthrene structure and ester bond and fluorine-containing dianhydride, and then mixes the component A and the component B; the introduction of a large number of fluorine groups enables the polyimide to have lower polarizability and larger free volume, and is also beneficial to reducing the dielectric constant of the polyimide; the thianthrene structure can improve the adhesion between polyimide and metal copper by utilizing the good affinity of thioether bonds and metal, and the thianthrene ring belongs to a rigid and planar structure, so that the thermal stability of the polyimide can be improved, and the thermal expansion coefficient of the polyimide can be reduced; the introduction of ester bonds can enhance intermolecular forces of the polyimide and reduce the thermal expansion coefficient of the polyimide. The dielectric constant and the thermal stability of the film are regulated and controlled by adjusting the proportion of the polyamic acid A and the polyamic acid B so as to meet the requirements of the application field on the polyimide film with low dielectric constant and high thermal stability.
Compared with other organic matters or inorganic matters, the polyimide film has better affinity by using the mode of blending the similar solutions, and is easy to stably prepare the polyimide film with excellent comprehensive performance. The preparation method of the blended polyimide provided by the invention has simple and various preparation processes and low requirement on conditions, thereby being suitable for industrial production.
Drawings
FIG. 1 is an infrared spectrum of a polyimide obtained in examples 2 to 4, wherein:
a corresponds to example 2;
b corresponds to example 3;
c corresponds to example 4;
FIG. 2 is a static thermomechanical analysis (TMA) plot of examples and comparative examples;
fig. 3 is a dynamic thermomechanical analysis (DMA) plot for the examples and comparative examples.
Detailed Description
The following examples are further explained and illustrated, but the present invention is not limited in any way by the specific examples. Unless otherwise indicated, the methods and equipment used in the examples are conventional in the art and all materials used are conventional commercially available materials.
Example 1
This example provides a method for preparing a diamine monomer (bis (4-aminophenyl) thianthrene-2,7-dicarboxylate, TDBDA) containing a thianthrene structure and an ester bond, comprising the steps of:
s1, synthesizing an intermediate thianthrene-2,7-dicarbonyl dichloride:
0.05mol of thianthrene-2,7-dicarboxylic acid is added into a three-neck flask, 100ml of dewatered dichloromethane is added, 17.846g of thionyl chloride is slowly dripped under the ice bath condition, then 3 to 4 drops of N, N-dimethylformamide are dripped as a catalyst, magnetic stirring is carried out, argon is introduced, and the temperature is raised to 75 ℃ for reaction reflux for 12 hours. The solvent and excess thionyl chloride were evaporated under reduced pressure to give 2,7-thianthrene dicarboxylic acid chloride as an intermediate. The intermediate has the following structure:
s2, synthesizing an intermediate bis (4-nitrophenyl) thianthrene-2,7-dicarboxylate:
dissolving 0.1mol of 4-nitroaniline in 150ml of a solution of N-methylpyrrolidone and pyridine 4:1, slowly adding 0.02mol of thianthrene-2,7-dicarbonyl dichloride, stirring for 2 hours at room temperature under an argon environment, heating to 100 ℃ for reaction for 12 hours, cooling, pouring the reaction liquid into methanol, filtering out precipitates, fully washing with the methanol, recrystallizing in N, N-dimethylformamide and water, and drying for 24 hours in a vacuum drying oven at 80 ℃ to obtain an intermediate bis (4-nitrophenyl) thianthrene-2,7-dicarboxylate. The intermediate has the following structure:
s3, synthesizing TDBDA:
putting 0.01mol bis (4-nitrophenyl) thianthrene-2,7-dicarboxylate into a three-neck flask, adding 450ml absolute ethyl alcohol, magnetically stirring and introducing argon, heating in oil bath to 70 ℃, adding 0.1g of 10-wt palladium carbon, gradually dropwise adding 10ml hydrazine hydrate, refluxing for 24h, filtering the reaction solution by using a funnel, placing the filtrate in a refrigerator for 24h to crystallize, collecting solid after suction filtration, and drying in a vacuum drying oven at 80 ℃ for 24h to obtain a diamine monomer, wherein the structure is as follows:
example 2
This example provides a method for preparing a low dielectric blended polyimide, comprising the steps of:
s1, adding 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether and hexafluoro dianhydride into a polar aprotic solvent protected by inert gas according to a molar ratio of 1:1, and stirring for reaction for 24 hours to obtain a 30wt% homogeneous and viscous polyamic acid glue solution A.
S2, adding TDBDA and hexafluoro dianhydride into a polar aprotic solvent protected by inert gas according to a molar ratio of 1:1, and stirring for reacting for 24 hours to obtain 30wt% homogeneous and viscous polyamic acid glue solution B.
And S3, mixing the polyamic acid glue solution A in the step S1 and the polyamic acid glue solution B in the step S2 in equal mass ratio, and stirring for 8 hours at 4 ℃ to obtain a blending type polyamic acid glue solution.
S4, uniformly coating the mixed polyamic acid glue solution obtained in the step S3 on clean glass, and performing thermal imidization on the polyamic acid glue solution, wherein the gradient of temperature rise is controlled as follows: heating the polyimide film to 100 ℃ at room temperature, keeping the temperature for 1 hour, heating the polyimide film to 200 ℃ from 100 ℃, keeping the temperature for 1 hour, heating the polyimide film to 300 ℃ from 200 ℃, keeping the temperature for 1 hour, heating the polyimide film to 420 ℃ from 300 ℃, keeping the temperature for 1 hour, and cooling to obtain the polyimide film.
Example 3
This example provides a method for preparing a low dielectric blended polyimide, comprising the steps of:
s1. The
4,4' - [1,4-phenylbis (oxy) ] bis [3- (trifluoromethyl) aniline ] and 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride were added to a polar aprotic solvent under inert gas protection in a molar ratio of 1:1, and reacted for 24 hours with stirring to obtain 30wt% of a homogeneous, viscous polyamic acid solution A.
S2, adding TDBDA and 9,9-bis (trifluoromethyl) -2,3,6,7-xanthene tetracarboxylic dianhydride into a polar aprotic solvent protected by inert gas according to a molar ratio of 1:1, and stirring for reaction for 24 hours to obtain a 30wt% homogeneous and viscous polyamic acid glue solution B.
And S3, mixing the polyamic acid glue solution A in the step S1 and the polyamic acid glue solution B in the step S2 in equal mass ratio, and stirring for 8 hours at 4 ℃ to obtain a blending type polyamic acid glue solution.
S4, uniformly coating the mixed polyamic acid glue solution obtained in the step S3 on clean glass, and performing thermal imidization on the polyamic acid glue solution, wherein the gradient of temperature rise is controlled as follows: and (3) heating the room temperature to 100 ℃, keeping the temperature for 1 hour, heating the room temperature to 200 ℃ from 100 ℃, keeping the temperature for 1 hour, heating the room temperature to 300 ℃, keeping the temperature for 1 hour, heating the room temperature to 420 ℃ from 300 ℃, keeping the temperature for 1 hour, and cooling to obtain the polyimide film.
Example 4
This example provides a method for preparing a low dielectric blended polyimide, comprising the steps of:
s1, adding 4,4' - ((perfluoropropane-2,2-diyl) bis (4,1-phenylene)) bis (oxy)) bis (3- (trifluoromethyl) aniline) (BAPHF) and hexafluoro dianhydride into an inert gas protected polar aprotic solvent according to a molar ratio of 1.
S2, adding TDBDA and hexafluoro dianhydride into a polar aprotic solvent protected by inert gas according to a molar ratio of 1:1, and stirring for reaction for 24 hours to obtain 30wt% of homogeneous and viscous polyamic acid glue solution B.
And S3, mixing the polyamic acid glue solution A in the step S1 and the polyamic acid glue solution B in the step S2 in equal mass ratio, and stirring for 8 hours at 4 ℃ to obtain a blending type polyamic acid glue solution.
S4, uniformly coating the mixed polyamic acid glue solution obtained in the step S3 on clean glass, and performing thermal imidization on the polyamic acid glue solution, wherein the gradient of temperature rise is controlled as follows: and (3) heating the room temperature to 100 ℃, keeping the temperature for 1 hour, heating the room temperature to 200 ℃ from 100 ℃, keeping the temperature for 1 hour, heating the room temperature to 300 ℃, keeping the temperature for 1 hour, heating the room temperature to 420 ℃ from 300 ℃, keeping the temperature for 1 hour, and cooling to obtain the polyimide film.
Example 5
The implementation provides a preparation method of low-dielectric blended polyimide, which has the same steps as those in the embodiment 2, and the difference is that the mass ratio of the polyamic acid glue solution a to the polyamic acid glue solution B in the embodiment is 6: 4.
Example 6
The implementation provides a preparation method of low-dielectric blended polyimide, which has the same steps as those of the embodiment 2, and the difference is that the mass ratio of the polyamic acid glue solution A to the polyamic acid glue solution B in the embodiment is 7: 3.
Comparative example 1
In this comparative example, 0.01mol of 2,2 '-bis (trifluoromethyl) -4,4' -diaminophenyl ether and 20ml of N, N-dimethylformamide were charged in a three-necked flask, argon gas was introduced, and after completely dissolving, 0.01mol of hexafluorodianhydride was added, and after stirring and reacting for 12 hours, a homogeneous, transparent and viscous polyamic acid solution was obtained.
And removing bubbles from the polyamic acid solution, coating the polyamic acid solution on a glass plate in a blade mode, placing the glass plate in a vacuum oven, vacuumizing, and performing gradient temperature rise, wherein the temperature rise is controlled as follows: heating the room temperature to 100 ℃, keeping the temperature for 1h, heating the temperature of 100 ℃ to 200 ℃, keeping the temperature for 1h, heating the temperature of 200 ℃ to 300 ℃, keeping the temperature for 1h, heating the temperature of 300 ℃ to 420 ℃, keeping the temperature for 1h, and cooling to obtain the polyimide film.
Comparative example 2
In this comparative example, 0.01mol of TDBDA and 20ml of N, N-dimethylformamide were added to a three-necked flask, argon gas was introduced, the mixture was stirred and completely dissolved, and then 0.01mol of hexafluorodianhydride was added, and the mixture was stirred and reacted for 12 hours to obtain a homogeneous, transparent and viscous polyamic acid solution.
And removing bubbles from the polyamic acid solution, coating the polyamic acid solution on a glass plate in a blade mode, placing the glass plate in a vacuum oven, vacuumizing, and performing gradient temperature rise, wherein the temperature rise is controlled as follows: heating the room temperature to 100 ℃, keeping the temperature for 1h, heating the temperature of 100 ℃ to 200 ℃, keeping the temperature for 1h, heating the temperature of 200 ℃ to 300 ℃, keeping the temperature for 1h, heating the temperature of 300 ℃ to 420 ℃, keeping the temperature for 1h, and cooling to obtain the polyimide film.
Comparative example 3
The implementation provides a preparation method of low-dielectric blended polyimide, which has the same steps as those of the embodiment 2, and the difference is that the mass ratio of the polyamic acid glue solution A to the polyamic acid glue solution B in the embodiment is 3: 7.
Examples of the experiments
1. Infrared spectroscopy detection
As can be seen from the infrared spectrum in FIG. 1, the polyimide prepared according to the present invention was found to be 1725cm -1 And 1780cm -1 The characteristic peaks are respectively symmetrical and asymmetrical stretching vibration of a C = O bond in an imide ring, and are 1365cm -1 The obvious C-N bond stretching vibration characteristic absorption peak is appeared at 1070cm -1 A C-S-C characteristic absorption peak of 1015cm appears nearby -1 A C-O-C characteristic absorption peak appears nearby, and the absorption peak is 3500-3300 cm -1 Between which no-NH appears 2 Which all show that the polyimides of examples 2,3 and 4 have been successfully synthesized.
2. Performance detection
The thermal expansion coefficient and the thermal property of the polyimide films of examples 2 to 6 and comparative examples 1 to 3 were measured, and the results of the measurement data are shown in table 1 below. Meanwhile, the polyimide films of examples 2 to 6 and comparative examples 1 to 3 were examined at room temperature at 10 ℃ respectively 3 Hz～10 7 The dielectric properties at Hz frequency were measured as shown in Table 2 below:
TABLE 1
TABLE 2
| Dielectric constant of | 10 3 Hz | 10 4 Hz | 10 5 Hz | 10 6 Hz | 10 7 Hz |
| Example 2 | 3.06 | 3.06 | 3.03 | 3.03 | 3.03 |
| Example 3 | 3.02 | 3.02 | 3.01 | 3.0 | 3.0 |
| Example 4 | 2.96 | 2.96 | 2.95 | 2.95 | 2.95 |
| Example 5 | 2.92 | 2.92 | 2.91 | 2.89 | 2.89 |
| Example 6 | 2.84 | 2.84 | 2.83 | 2.83 | 2.83 |
| Comparative example 1 | 2.56 | 2.56 | 2.55 | 2.54 | 2.54 |
| Comparative example 2 | 3.34 | 3.34 | 3.32 | 3.33 | 3.33 |
| Comparative example 3 | 3.14 | 3.14 | 3.13 | 3.12 | 3.12 |
As can be seen from tables 1 and 2 and fig. 2 to 3, a single fluorine-containing diamine or a polyimide synthesized from a thianthrene structure, an ester bond and a dianhydride cannot have good low dielectric properties and thermal stability at the same time.
Example 8
The embodiment provides a preparation method of a glue-free flexible copper-clad plate, which comprises the steps of respectively taking the blended polyamide acid glue solutions prepared in the embodiments 2-6, scraping and coating the mixed polyamide acid glue solutions on a copper plate after bubbles are eliminated, then placing the copper plate in a vacuum oven, vacuumizing, raising the temperature by program for thermal imidization, and cooling to obtain the glue-free flexible copper-clad plate.
The peel strength of the polyimide film and the copper plate of the prepared adhesive-free flexible copper clad laminate is respectively detected, and the detection results are shown in the following table 3:
TABLE 3
As can be seen from table 3, the polyimide prepared by the present invention not only has good low dielectric properties and high heat stability, but also improves the adhesion property between the polyimide and the metal and the peel strength between the polyimide film and the metal substrate through the thianthrene structure in the molecular structure.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A preparation method of low dielectric blended polyimide is characterized by comprising the following preparation steps:
s1, adding fluorine-containing diamine and fluorine-containing dianhydride into a polar aprotic solvent protected by inert gas in proportion, and stirring for reaction to obtain a homogeneous and viscous polyamide acid glue solution A;
s2, adding diamine containing a thianthrene structure and an ester bond and fluorine-containing dianhydride into a polar aprotic solvent protected by inert gas in proportion, and stirring for reaction to obtain a homogeneous and viscous polyamide acid glue solution B;
s3, mixing the polyamic acid glue solution A in the step S1 and the polyamic acid glue solution B in the step S2 together in proportion, controlling the temperature to be minus 10-40 ℃, and stirring for 4-12 hours to prepare a blending type polyamic acid glue solution;
and S4, uniformly coating the mixed polyamic acid glue solution obtained in the step S3 on clean glass, and imidizing the polyamic acid glue solution to obtain the polyimide film.
2. The method for preparing low dielectric blended polyimide according to claim 1, wherein the fluorine-containing diamine in step S1 is one or more of the following structures:
the fluorine-containing dianhydride monomer is one or more of the following structures:
3. the method for preparing a low dielectric blended polyimide according to claim 1, wherein the diamine structure containing a thianthrene structure and an ester bond in step S2 is:
the fluorine-containing dianhydride monomer is one or more of the following structures:
4. the method for preparing a low dielectric blended polyimide according to claim 1, wherein the molar ratio of the fluorine-containing diamine monomer to the dianhydride monomer in step S1 is 1.
5. The method for preparing the low dielectric blended polyimide according to claim 1, wherein the strongly polar aprotic organic solvent in steps S1 and S2 is one or more selected from N-methylpyrrolidone, dimethylsulfoxide, dimethylsulfone, sulfolane, 1,4-dioxane, N-dimethylacetamide, N-dimethylformamide, m-cresol, and tetrahydrofuran.
6. The method for preparing a low dielectric blended polyimide film according to claim 1, wherein the mass ratio of the polyamic acid solution A to the polyamic acid solution B in the step S3 is 50-99.
7. The method for preparing low dielectric blended polyimide according to claim 1, wherein the mass fraction of the total mass of the diamine and the dianhydride in steps S1 and S2 to the total mass of the reaction materials is 2 to 50%.
8. The method for preparing low dielectric blended polyimide according to claim 1, wherein the stirring reaction time in step S1 is 0.5 to 72 hours; the stirring reaction time in the step S2 is 0.5-72 h.
9. The method of claim 1, wherein the imidization in step S4 comprises thermal imidization or chemical imidization.
10. The polyimide prepared by the preparation method of the low dielectric blended polyimide according to any one of claims 1 to 9, wherein the polyimide is applied to the field of microelectronics.
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