A low-dielectric polyimide film with a large volume, a preparation method and applications thereof

Abstract

The present application relates to polyimide film material technical field, specifically to a kind of super volume low dielectric polyimide film, preparation method and application;The preparation method of the super volume low dielectric polyimide film includes the following steps: step one, preparation and purification are obtained compound I;Step two, compound I and diamine are dissolved and dispersed in solution;Step three, after compound I and diamine are completely dissolved, add dianhydride monomer to obtain polyamide acid resin solution;Step four, after mixing, polyamide acid resin solution is placed in vacuum oven and defoaming;Step five, after defoaming, polyamide acid resin solution is extruded to mirror surface steel belt through die and forms self-supporting film;Step six, self-supporting film is subjected to imidization furnace and longitudinal tension, transverse tension imidization treatment simultaneously to obtain polyimide film;Step seven, polyimide film is wound by winding machine, and is cut according to requirements by slitting machine on-line detection, and finally packaged into warehouse.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of polyimide film materials, in particular to a large-volume low-dielectric polyimide film, a preparation method and application thereof. BACKGROUND

[0002] In recent years, with the rapid development of high-speed communication field, the application size of electronic components tends to miniaturization, the chip integration in large-scale integrated circuits is significantly improved, and the interconnection line density of the chip is increased, which increases the resistance in the line and the capacitance in the wiring, generates signal resistance-capacitance delay effect, and affects the signal transmission speed and signal loss, which has become a new fetter for the development of integrated circuits in the direction of high speed, high density, low energy consumption and multi-function.

[0003] Therefore, in order to meet the requirements of high integration of integrated circuits and improve the transmission speed of signals, high-density signal lines in the package require to maintain electrical insulation between each other, and a dielectric material with as low dielectric constant as possible should be selected as the interlayer insulating material of integrated circuits to ensure that the minimum electrical interaction signals can be normally transmitted in adjacent lines.

[0004] Polyimide is widely used in electronic materials, aerospace, communication, national defense and military fields due to its good heat resistance, corrosion resistance, insulation and excellent mechanical properties. Polyimide has high-temperature cycle use performance, good self-lubricating performance, excellent mechanical properties, UL94 level flame retardant grade, good radiation resistance, stable insulation performance, good dielectric performance, and a dielectric constant of about 3.4. By introducing fluorine elements into the polyimide system or dispersing nano-sized particles in the polyimide, the dielectric constant can be reduced to about 2.8, and the dielectric loss can be reduced to below 0.006. Therefore, in order to meet the requirements of 5G high frequency and high speed, people choose polyimide material as an important layer dielectric material, and it is particularly important to reduce the dielectric constant and dielectric loss of PI. SUMMARY

[0005] In view of the deficiencies of the prior art, the purpose of the present application can be achieved by the following technical solutions:

[0006] A diamine compound I, the structural formula of which is as follows:

[0007] .

[0008] A preparation method of a diamine compound I, the preparation method comprising the following steps:

[0009] S1, 4-bromoanthrone and 4-trifluoromethylphenylboronic acid are added to a flask and mixed, THF is added to dissolve the reaction; then K2CO3 aqueous solution and methyltrioctylammonium chloride are added, the mixture is stirred at room temperature under argon atmosphere; then tetraphenylphosphonium palladium is added as a catalyst, and the reaction mixture is stirred at 344K; after cooling to room temperature, the product is concentrated and purified by silica gel column chromatography;

[0010] S2, 2-bromo-1-bromomethyl-4-ethylbenzene and triethyl phosphite are added to a flask and mixed, stirred at 423K under argon atmosphere; then the mixture is cooled to room temperature, the compound obtained after purification in step one, THF and potassium tert-butoxide are added, the reaction mixture is stirred at room temperature; after the reaction, the product is concentrated and purified by silica gel column chromatography;

[0011] S3, the compound obtained after purification in step two and 4-aminophenylboronic acid are added to a flask and mixed, THF is added to dissolve the reaction; K2CO3 aqueous solution and methyltrioctylammonium chloride are added, the mixture is stirred at room temperature under argon atmosphere; then tetraphenylphosphonium palladium is added as a catalyst, and the reaction mixture is stirred at 344K; after cooling to room temperature, the product is concentrated and purified by silica gel column chromatography;

[0012] S4, the compound obtained after purification in step three and p-fluoronitrobenzene and cesium fluoride are added to a flask and mixed, DMSO is added to dissolve the reaction; stirred at 423K under argon atmosphere, after cooling to room temperature, the product is concentrated and purified by silica gel column chromatography;

[0013] S5, the compound obtained after purification in step four, 10% Pd / C catalyst, hydrazine monohydrate are added to a flask and mixed, ethanol is added to dissolve the reaction, stirred at 354K under argon atmosphere, then the mixture is filtered to remove the Pd / C catalyst; after the mixture is cooled to room temperature, the precipitated crystals are separated by filtration, recrystallized twice with ethanol, ground into powder and dried under vacuum, finally the compound I is obtained.

[0014] Further, the molar ratio of 4-bromoanthrone, 4-trifluoromethylphenylboronic acid, 2-bromo-1-bromomethyl-4-ethylbenzene, triethyl phosphite, potassium tert-butoxide, 4-aminophenylboronic acid, p-fluoronitrobenzene and cesium fluoride is 8:9:10:30:15:4:8:8.

[0015] A preparation method of a large-volume low-dielectric polyimide film, the preparation method comprising the following steps:

[0016] Step one, the compound I is prepared and purified according to the method described above;

[0017] Step two, compound I and diamine monomer are dissolved and dispersed in an organic solvent;

[0018] Step three, after compound I and diamine monomer are completely dissolved, dianhydride monomer is added to react to obtain a polyamic acid resin solution;

[0019] Step four, the mixed polyamic acid resin solution is placed in a vacuum oven for defoaming;

[0020] Step five, the defoamed polyamic acid resin solution is extruded onto a mirror surface steel belt through a die to form a self-supporting film;

[0021] Step six, the self-supporting film is subjected to imidization treatment by longitudinal and transverse stretching through an imidization furnace to obtain a polyimide film;

[0022] Step seven, the polyimide film is wound by a winding machine, detected online by a slitting machine and cut according to requirements, and finally packaged and stored.

[0023] Further, the molar mass ratio of the diamine monomer and the dianhydride monomer is 1: (1-1.2); the mass ratio of the sum of the diamine monomer and the dianhydride monomer to the mass of the organic solvent is (1.5-2.5):10.

[0024] Further, the organic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

[0025] Further, the dianhydride monomer is one or more of BPDA, BPADA, PMDA, 6FDA and BTDA.

[0026] Further, the diamine monomer is one of RODA, TFDB and PDA.

[0027] The above-mentioned preparation method of the ultra-large volume low dielectric polyimide film is applied to the field of communication.

[0028] The present application has the advantages that a diamine compound with an ultra-large volume structure is introduced into the polymer molecular chain, which can effectively reduce the dielectric constant on the one hand, and the asymmetric structure can further reduce the dielectric loss on the other hand. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, for those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.

[0030] Figure 1 Flow chart for preparation of diamine compound I monomer in the present application;

[0031] Figure 2 NMR chart for sample monomer in the present application; DETAILED DESCRIPTION

[0032] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without any creative effort fall within the protection scope of the present application.

[0033] A preparation method of a diamine compound I, the preparation method comprising the following steps:

[0034] S1, 4-bromoadamantone (10.93 g, 0.04 mol) and 4-trifluoromethylphenylboronic acid (8.55 g, 0.045 mol) were added to a 500 mL flask for mixing, and 400 ml THF was added for dissolution reaction. Then 2M aqueous K2CO3 solution (120 mL) and 10 drops of methyltrioctylammonium chloride were added, and the mixture was stirred at room temperature under argon atmosphere for 45 minutes. Then tetrakis(triphenylphosphine)palladium was added as a catalyst, and the reaction mixture was stirred at 344K for 24 hours. After cooling to room temperature, the product was concentrated, and purified by silica gel column chromatography.

[0035] S2, 2-bromo-1-bromomethyl-4-ethylbenzene (13.90 g, 0.05 mol) and triethyl phosphite (24.92 g, 0.15 mol) were added to a 500 mL flask for mixing, and stirred at 423K under argon atmosphere for 24 hours. Then the mixture was cooled to room temperature, and the compound obtained after purification in step one, 400 mL THF and potassium tert-butoxide (8.42 g, 0.075 mol) were added, and the reaction mixture was stirred at room temperature for 12 hours. After reaction, the product was concentrated, and purified by silica gel column chromatography.

[0036] S3, the compound obtained after purification in step two and 4-aminophenylboronic acid (3.47 g, 0.02 mmol) were mixed in a 250 mL flask and dissolved in 100 mL THF. Then, 2M aqueous K2CO3 solution (30 mL) and 10 drops of methyltrioctylammonium chloride were added, and the mixture was stirred at room temperature under argon atmosphere for 45 minutes. Subsequently, tetrakis(triphenylphosphine)palladium was added as a catalyst, and the reaction mixture was stirred at 344 K for 24 hours. After cooling to room temperature, the product was concentrated and purified by silica gel column chromatography.

[0037] S4, the compound obtained after purification in step three and p-fluoronitrobenzene (5.64 g, 0.04 mol) and cesium fluoride (6.08 g, 0.04 mol) were mixed in a 250 mL flask and dissolved in 150 mL DMSO. Stirring was performed at 423 K under argon atmosphere for 24 hours, and after cooling to room temperature, the product was concentrated and purified by silica gel column chromatography.

[0038] S5, the compound obtained after purification in step four, 10% Pd / C catalyst (0.5 g), and hydrazine monohydrate (16 mL) were mixed in a 500 mL flask and dissolved in 300 mL ethanol. Stirring was performed at 354 K under argon atmosphere for 24 hours, and then the mixture was filtered to remove the Pd / C catalyst. After the mixture was cooled to room temperature, the precipitated crystals were separated by filtration, recrystallized twice with ethanol, ground into a powder, and dried under vacuum, finally obtaining compound I.

[0039] The structural formula of the compound I is as follows:

[0040] .

[0041] Example 1:

[0042] The preparation method of the large-volume low-dielectric polyimide film provided by the embodiment comprises the following steps: step one, preparing and purifying compound I; step two, dissolving and dispersing compound I and other diamines in a solution, wherein the other diamines are selected from RODA, and the solvent is N,N-dimethylacetamide; step three, after compound I and the other diamines are completely dissolved, batch adding dianhydride monomers, the dianhydride is selected from BTDA and 6FDA, the reaction temperature is controlled to be 0-10℃, and the reaction time is 6-24 hours, so that a uniform viscous polyamide acid solution with a certain solid content is obtained, and the resin viscosity is controlled to be 100-250 Pa·s; step four, placing the mixed polyamide acid resin in an oven and applying vacuum for defoaming treatment, and the specific defoaming time is 12 hours; step five, pressing the defoamed polyamide acid resin into a die head through a pipeline, adjusting the thickness of the die head, and uniformly flowing the resin to a mirror surface steel belt, the casting machine box temperature is controlled to be 150±10℃, the casting speed is 5 m / min, the air speed is controlled, most of the solvent is evaporated to obtain a self-supporting film with uniform thickness; step six, drawing and pressing the self-supporting film after casting into a clamp plate, and entering an imidization furnace, and the temperature is increased from room temperature to 60-80℃, and then kept for 0.5-1 hours; then the temperature is increased to 100-130℃, and then kept for 0.5-1 hours; then the temperature is increased to 160-180℃, and then kept for 0.5-1 hours; then the temperature is increased to 200-220℃, and then kept for 0.5-1 hours; then the temperature is increased to 250-270℃, and then kept for 0.5-1 hours; then the temperature is increased to 290-320℃, and then kept for 0.5-1 hours; step seven, winding the polyimide film through a winding machine, detecting online through a slitting machine and slitting according to requirements, and finally packaging and storing in a warehouse.

[0043] The polyimide film obtained by the embodiment has excellent dielectric properties, and also has mechanical and thermodynamic properties, and can be applied to the field of 5G communication. Specifically, the film thickness is 30±5 μm, the dielectric constant is 2.5, the dielectric loss is 0.004, the tensile strength is 144 MPa, the elongation at break is 17%, the elastic modulus is 3.9 GPa, the Tg is about 302℃, and the thermal expansion coefficient is 46 ppm / K.

[0044] Example 2:

[0045] The preparation method of the large-volume low-dielectric polyimide film provided by the embodiment comprises the following steps: step one, preparing and purifying compound I; step two, dissolving and dispersing compound I and other diamines in a solution, wherein the other diamines are selected from TFDB, and the solvent is N,N-dimethylacetamide; step three, after compound I and the other diamines are completely dissolved, batch adding dianhydride monomers, the dianhydride is selected from BPDA and BPADA, the reaction temperature is controlled to be 0-10 ℃, and the reaction time is 6-24 hours, so that a uniform viscous polyamide acid solution with a certain solid content is obtained, and the resin viscosity is controlled to be 100-250 Pa·s; step four, placing the mixed polyamide acid resin in an oven and applying vacuum for defoaming treatment, and the specific defoaming time is 12 hours; step five, pressing the defoamed polyamide acid resin into a die head through a pipeline, adjusting the thickness of the die head, and uniformly flowing the resin to a mirror surface steel belt, the casting machine box temperature is controlled to be 150±10 ℃, the casting speed is 5 m / min, the air speed is controlled, most of the solvent is evaporated to obtain a self-supporting film with uniform thickness; step six, pulling and pressing the self-supporting film after casting into a clamp plate, and entering an imidization furnace, and the temperature is increased from room temperature to 60-80 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 100-130 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 160-180 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 200-220 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 250-270 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 290-320 ℃, and then kept for 0.5-1 hours; step seven, winding the polyimide film through a winding machine, detecting online through a slitting machine and slitting according to requirements, and finally packaging and warehousing.

[0046] The polyimide film obtained by the embodiment has excellent dielectric properties, and also has mechanical and thermodynamic properties, and can be applied to the field of 5G communication. Specifically, the film thickness is 30±5 μm, the dielectric constant is 2.4, the dielectric loss is 0.003, the tensile strength is 139 MPa, the elongation at break is 19%, the elastic modulus is 4.1 GPa, the Tg is about 307 ℃, and the thermal expansion coefficient is 41 ppm / K.

[0047] Example 3:

[0048] The preparation method of the large-volume low-dielectric polyimide film provided by the embodiment comprises the following steps: Step 1, preparing and purifying compound I; Step 2, dissolving and dispersing compound I and other diamines in a solution, wherein the other diamines are selected from TFDB and PDA, and the solvent is N,N-dimethylacetamide; Step 3, after compound I and the other diamines are completely dissolved, batch adding dianhydride monomers, and the dianhydride is selected from BPDA and PMDA, the reaction temperature is controlled to be 0-10 ℃, and the reaction time is 6-24 hours, so as to obtain a uniform viscous polyamic acid solution with a certain solid content, and the resin viscosity is controlled to be 100-250 Pa·s; Step 4, placing the mixed polyamic acid resin in an oven and performing defoaming treatment under vacuum, and the specific defoaming time is 12 hours; Step 5, pressing the defoamed polyamic acid resin into a die head through a pipeline, adjusting the thickness of the die head, and uniformly flowing the resin to a mirror surface steel belt, the casting machine box temperature is controlled to be 150±10 ℃, the casting speed is 5 m / min, the air speed is controlled, most of the solvent is evaporated, and a self-supporting film with uniform thickness is obtained; Step 6, pulling and pressing the cast self-supporting film into a clamp plate, and entering an imidization furnace, and the temperature is increased from room temperature to 60-80 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 100-130 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 160-180 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 200-220 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 250-270 ℃, and then kept for 0.5-1 hours; then the temperature is increased to 290-320 ℃, and then kept for 0.5-1 hours. Step 7, winding the polyimide film through a winding machine, detecting online through a slitting machine, and finally packaging and storing.

[0049] The polyimide film obtained by the embodiment has excellent dielectric properties, and also has mechanical and thermodynamic properties, and can be applied to the field of 5G communication. Specifically, the film thickness is 30±5 μm, the dielectric constant is 2.6, the dielectric loss is 0.005, the tensile strength is 148 MPa, the elongation at break is 14%, the elastic modulus is 4.3 GPa, the Tg is about 310 ℃, and the thermal expansion coefficient is 39 ppm / K.

[0050] Comparative Example 1

[0051] Comparative Example 1 and Example 1 are compared, the other diamines are selected from RODA, the solvent is N,N-dimethylacetamide; and the dianhydride monomers are batch added, and the dianhydride is BTDA and 6FDA. The final performance of the film is that the film thickness is 30±5 μm, the dielectric constant is 2.9, the dielectric loss is 0.009, the tensile strength is 138 MPa, the elongation at break is 15%, the elastic modulus is 3.7 GPa, the Tg is about 300 ℃, and the thermal expansion coefficient is 47 ppm / K.

[0052] In the description of the specification, the description of the terms "one embodiment", "an example", "a specific example" and the like means that the specific features, structures, materials or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In the specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Also, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0053] The basic principles, main features and advantages of the present application are shown and described above. Those skilled in the art should understand that the present application is not limited by the above embodiments, and the above embodiments and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application.

Claims

1. A diamine compound I characterized in that, The structural formula of the diamine compound I is as follows: 。 2. A process for the preparation of a diamine compound I according to claim 1, characterized in that, The preparation method comprises the following steps: S1, 4-bromo anthrone and 4-trifluoromethyl phenyl boronic acid are added to a flask for mixing, THF is added for dissolution reaction; then K2CO3 aqueous solution and methyltrioctylammonium chloride are added, the mixture is stirred at room temperature under an argon atmosphere; then tetrakis triphenylphosphine palladium is added as a catalyst, and the reaction mixture is stirred at 344K; after cooling to room temperature, the product is concentrated, and purified by silica gel column chromatography; S2, 2-bromo-1-bromomethyl-4-ethyl benzene and triethyl phosphite are added to a flask for mixing, and stirred at 423K under an argon atmosphere; then the mixture is cooled to room temperature, the compound obtained after purification in step one, THF and potassium tert-butoxide are added, and the reaction mixture is stirred at room temperature; after reaction, the product is concentrated, and purified by silica gel column chromatography; S3, the compound obtained after purification in step two and 4-aminophenyl boronic acid are added to a flask for mixing, THF is added for dissolution reaction; K2CO3 aqueous solution and methyltrioctylammonium chloride are added, and the mixture is stirred at room temperature under an argon atmosphere; then tetrakis triphenylphosphine palladium is added as a catalyst, and the reaction mixture is stirred at 344K; after cooling to room temperature, the product is concentrated, and purified by silica gel column chromatography; S4, the compound obtained after purification in step three and p-fluoro nitrobenzene and cesium fluoride are added to a flask for mixing, DMSO is added for dissolution reaction; stirring is carried out at 423K under an argon atmosphere, and after cooling to room temperature, the product is concentrated, and purified by silica gel column chromatography; S5, the compound obtained after purification in step four, 10% Pd / C catalyst and hydrazine monohydrate are added to a flask for mixing, ethanol is added for dissolution reaction, stirring is carried out at 354K under an argon atmosphere, and then the mixture is filtered to remove the Pd / C catalyst; after the mixture is cooled to room temperature, the precipitated crystals are separated by filtration, recrystallized twice with ethanol, ground into powder, and dried under vacuum, finally obtaining the compound I.

3. The process for the preparation of a diamine compound I according to claim 2, characterized in that, The molar ratio of 4-bromo anthrone, 4-trifluoromethyl phenyl boronic acid, 2-bromo-1-bromomethyl-4-ethyl benzene, triethyl phosphite, potassium tert-butoxide, 4-aminophenyl boronic acid, p-fluoro nitrobenzene and cesium fluoride is 8:9:10:30:15:4:8:

8.

4. A method for producing a low dielectric polyimide film of an ultra large volume, characterized by, The preparation method comprises the following steps: Step one, the compound I is prepared and purified according to the method in claim 2; Step two, the compound I and the diamine monomer are dissolved and dispersed in an organic solvent; Step three, after the compound I and the diamine monomer are completely dissolved, the dianhydride monomer is added for reaction to obtain a polyamic acid resin solution; Step four, the mixed polyamic acid resin solution is placed in a vacuum oven for defoaming; Step five, the defoamed polyamic acid resin solution is extruded through a die head onto a mirror surface steel belt to form a self-supporting film; Step six, the self-supporting film is subjected to imidization treatment by an imidization furnace while being longitudinally and transversely stretched to obtain a polyimide film; Step seven, polyimide film through the winding machine winding, through the slitting machine online detection and according to the requirements of the cutting, finally packaging into the warehouse.

5. The process for the preparation of a diamine compound I according to claim 4, characterized in that, The molar mass ratio of the diamine monomer and the dianhydride monomer is 1:(1-1.2); the sum of the mass of the diamine monomer and the dianhydride monomer and the mass of the organic solvent is (1.5-2.5):

10.

6. The process for the preparation of a diamine compound I according to claim 4, characterized in that, The organic solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone.

7. The process for the preparation of a diamine compound I according to claim 4, characterized in that, The dianhydride monomer is one or more of BPDA, BPADA, PMDA, 6FDA and BTDA.

8. The method of claim 4, wherein the low dielectric polyimide film has a thickness of 100 μm or more. The diamine monomer is one of RODA, TFDB and PDA.

9. The application of the ultra-large volume low dielectric polyimide film prepared by the method of any one of claims 4-8 in the field of communication.

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