Ultra-large-volume low-dielectric polyimide film as well as preparation method and application of ultra-large-volume low-dielectric polyimide film

Abstract

The invention relates to the technical field of polyimide film materials, in particular to an ultra-large-volume low-dielectric polyimide film, a preparation method and application. The preparation method of the ultra-large-volume low-dielectric polyimide film comprises the following steps: step 1, preparing and purifying to obtain a compound I; 2, dissolving and dispersing a compound I and diamine in a solution; 3, after the compound I and diamine are completely dissolved, dianhydride monomers are added for a reaction, and a polyamide acid resin solution is obtained; step 4, placing the mixed polyamide acid resin solution in a vacuum oven for defoaming; 5, casting the defoamed polyamide acid resin solution to the mirror surface steel belt through a die head to form a self-supporting film; 6, the self-supporting film is subjected to longitudinal drawing and transverse drawing imidization treatment through an imidization furnace at the same time, and a polyimide film is obtained; 7, the polyimide film is wound through a winding machine, online detection is conducted through a splitting machine, splitting is conducted according to requirements, and finally packaging and warehousing are conducted.

Description

Technical Field

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

[0002] In recent years, with the rapid development of high-speed communications, the application size of electronic components has been miniaturized, the chip integration in large-scale integrated circuits has been significantly improved, and the density of chip interconnections has increased, which has increased the resistance in the lines and the capacitance in the wiring, resulting in signal resistance-capacitance delay effects, affecting signal transmission speed and signal loss. This has become a new shackle for the development of integrated circuits towards high speed, high density, low energy consumption and multi-functions.

[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 are required to maintain electrical insulation from each other. Dielectric materials with the lowest possible dielectric constant value should be selected as interlayer insulation materials for integrated circuits to ensure that the minimum electrical interaction signal can be transmitted normally in adjacent lines.

[0004] Polyimide is widely used in electronic materials, aerospace, communications, national defense and military fields due to its good heat resistance, corrosion resistance, insulation and excellent mechanical properties. Polyimide has high temperature cyclic performance, good self-lubricating performance, excellent mechanical properties, flame retardant grade up to UL94, good radiation resistance, stable insulation performance, good dielectric properties, and a dielectric constant of about 3.4. By introducing fluorine elements into the polyimide system or dispersing nano-sized particles in 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 high frequency and high speed requirements of 5G, people choose polyimide materials as important layer dielectric materials, and it is particularly important to reduce the dielectric constant and dielectric loss of PI. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention can be achieved through the following technical solutions:

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

[0007]

[0008] A method for preparing a diamine compound I, comprising the following steps:

[0009] S1. Add 4-bromoanthrone and 4-trifluoromethylphenylboric acid into a flask and mix them, add THF for dissolution reaction; then add K2CO3 aqueous solution and methyltrioctylammonium chloride, and stir the mixture under argon atmosphere at room temperature; then add tetrakistriphenylphosphine palladium as a catalyst, and stir the reaction mixture at 344K; after cooling to room temperature, concentrate the product and purify it by silica gel column chromatography;

[0010] S2, adding 2-bromo-1-bromomethyl-4-ethylbenzene and triethyl phosphite into a flask for mixing, and stirring at 423K under an argon atmosphere; then cooling the mixture to room temperature, adding the compound obtained after purification in step 1, THF and potassium tert-butoxide, and stirring the reaction mixture at room temperature; after the reaction, concentrating the product, and purifying it by silica gel column chromatography;

[0011] S3, adding the compound obtained after purification in step 2 and 4-aminophenylboronic acid into a flask for mixing, adding THF for dissolution reaction; adding K2CO3 aqueous solution and methyltrioctylammonium chloride, stirring the mixture at room temperature under argon atmosphere; then adding tetrakistriphenylphosphine palladium as a catalyst, and stirring the reaction mixture at 344K; after cooling to room temperature, concentrating the product, and purifying it by silica gel column chromatography;

[0012] S4, adding the compound obtained after purification in step 3, p-fluoronitrobenzene and cesium fluoride into a flask for mixing, adding DMSO for dissolution reaction; stirring under argon atmosphere at 423K, cooling to room temperature, concentrating the product, and purifying it by silica gel column chromatography;

[0013] S5. Add the compound obtained after purification in step 4, 10% Pd / C catalyst, and hydrazine monohydrate into a flask for mixing, add ethanol for dissolution reaction, stir at 354K under argon atmosphere, and then filter the mixture to remove the Pd / C catalyst; after the mixture is cooled to room temperature, separate the precipitated crystals by filtration, recrystallize twice with ethanol, grind into powder, and dry under vacuum to finally obtain compound I.

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

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

[0016] Step 1, preparing and purifying compound I according to the method described in claim 2;

[0017] Step 2, dissolving and dispersing compound I and diamine monomer in an organic solvent;

[0018] Step 3: After the compound I and the diamine monomer are completely dissolved, a dianhydride monomer is added to react to obtain a polyamic acid resin solution;

[0019] Step 4: placing the mixed polyamic acid resin solution in a vacuum oven for defoaming;

[0020] Step 5, the defoamed polyamic acid resin solution is flowed through a die head onto a mirror steel belt to form a self-supporting film;

[0021] Step 6: The self-supporting film is subjected to imidization treatment by longitudinal and transverse imidization in an imidization furnace to obtain a polyimide film;

[0022] Step 7: The polyimide film is rolled up by a winder, inspected online by a slitting machine, slit as required, and finally packaged and put into storage.

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

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

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

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

[0027] The ultra-large volume low dielectric polyimide film prepared by the above-mentioned method for preparing an ultra-large volume low dielectric polyimide film is applied in the communication field.

[0028] Beneficial effects of the present invention: The present invention proposes an ultra-large volume low dielectric polyimide film and a preparation method thereof, which has the advantage of introducing a diamine compound with an ultra-large volume structure into the polymer molecular chain. On the one hand, the unit with a larger free volume can effectively reduce the dielectric constant, and on the other hand, its asymmetric structure can further reduce the dielectric loss. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, for ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 This is a flow chart for preparing the diamine compound I monomer in the present invention;

[0031] Figure 2 This is the nuclear magnetic resonance characterization image of the sample monomer of the present invention; DETAILED DESCRIPTION

[0032] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0033] A method for preparing a diamine compound I, comprising the following steps:

[0034] S1, 4-bromoanthrone (10.93g, 0.04mol) and 4-trifluoromethylphenylboric acid (8.55g, 0.045mol) are joined in the 500mL flask and mix, add 400ml THF and carry out dissolution reaction.Then add the K of 2M CO The aqueous solution (120mL) and 10 methyl trioctyl ammonium chlorides, at room temperature under argon atmosphere, stirred mixture 45 minutes.Add tetrakis triphenylphosphine palladium as catalyzer subsequently, and reaction mixture was stirred 24 hours under 344K.After being cooled to room temperature, product is concentrated, and is purified by silica gel column chromatography.

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

[0036] S3, compound gained after step 2 purifying and 4-aminophenylboric acid (3.47g, 0.02mmol) join in 250mL flask and mix, add 100mL THF and carry out dissolution reaction.Then, add the K of 2M CO The aqueous solution (30mL) and 10 methyl trioctyl ammonium chlorides, at room temperature under argon atmosphere, stirred mixture 45 minutes.Add tetrakis triphenylphosphine palladium as catalyzer subsequently, and reaction mixture was stirred 24 hours at 344K.After being cooled to room temperature, product is concentrated, and is purified by silica gel column chromatography.

[0037] S4, the compound obtained after purification in step 3, p-fluoronitrobenzene (5.64g, 0.04mol) and cesium fluoride (6.08g, 0.04mol) were added to a 250mL flask for mixing, and 150mL DMSO was added for dissolution reaction. Stirred for 24 hours under argon atmosphere at 423K, cooled to room temperature, concentrated the product, and purified by silica gel column chromatography.

[0038] S5. The compound obtained after purification in step 4, 10% Pd / C catalyst (0.5 g), and hydrazine monohydrate (16 mL) were added to a 500 mL flask for mixing, 300 ml of ethanol was added for dissolution reaction, and stirred 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 powder, and dried under vacuum to finally obtain compound I.

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

[0040]

[0041] Embodiment 1:

[0042] The present embodiment provides a method for preparing a large-volume low-dielectric polyimide film, comprising the following steps: step 1, preparing and purifying compound I; step 2, dissolving compound I and other diamines in a solution, wherein other diamines are selected from RODA and solvents are selected from N,N-dimethylacetamide; step 3, after compound I and other diamines are completely dissolved, dianhydride monomers are added in batches, wherein dianhydrides are selected from BTDA and 6FDA, the reaction temperature is controlled at 0-10° C., the reaction time is 6-24 hours, and a uniform and viscous polyamic acid solution with a certain solid content is obtained, and the resin viscosity is controlled at 100-250 Pa·s; step 4, placing the mixed polyamic acid resin in an oven, and applying vacuum for defoaming treatment, wherein the specific defoaming time is 12 hours; step 5, The defoamed polyamic acid resin is pressed into the die through a pipeline, and the thickness of the die is adjusted to make the resin evenly flow onto the mirror steel belt. The temperature of the flow box is controlled at 150±10°C, the flow speed is 5m / min, and the wind speed is controlled to evaporate most of the solvent to obtain a self-supporting film with uniform thickness; Step six is ​​to pull and press the self-supporting film after the flow into a clamping plate, enter the imidization furnace, heat it from room temperature to 60-80°C, and keep it warm for 0.5-1h; then heat it to 100-130°C, and keep it warm for 0.5-1h; then heat it to 160-180°C, and keep it warm for 0.5-1h; then heat it to 200-220°C, and keep it warm for 0.5-1h; then heat it to 250-270°C, and keep it warm for 0.5-1h; then heat it to 290-320°C, and keep it warm for 0.5-1h. ; Step seven is to wind the polyimide film through a winder, conduct online inspection through a slitting machine, slit it as required, and finally pack it for storage.

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

[0044] Embodiment 2:

[0045] The present embodiment provides a method for preparing a large-volume low-dielectric polyimide film, comprising the following steps: step 1, preparing and purifying compound I; step 2, dissolving compound I and other diamines in a solution, wherein other diamines are selected from TFDB, and the solvent is N,N-dimethylacetamide; step 3, after compound I and other diamines are completely dissolved, dianhydride monomers are added in batches, wherein dianhydrides are selected from BPDA and BPADA, the reaction temperature is controlled at 0-10° C., the reaction time is 6-24 hours, and a uniform and viscous polyamic acid solution with a certain solid content is obtained, and the resin viscosity is controlled at 100-250 Pa·s; step 4, placing the mixed polyamic acid resin in an oven, and applying vacuum for defoaming treatment, wherein the specific defoaming time is 12 hours; step 5, The defoamed polyamic acid resin is pressed into the die through a pipeline, and the thickness of the die is adjusted to make the resin evenly flow onto the mirror steel belt. The temperature of the flow box is controlled at 150±10°C, the flow speed is 5m / min, and the wind speed is controlled to evaporate most of the solvent to obtain a self-supporting film with uniform thickness; Step six is ​​to pull and press the self-supporting film after the flow into a clamping plate, enter the imidization furnace, heat it from room temperature to 60-80°C, and keep it warm for 0.5-1h; then heat it to 100-130°C, and keep it warm for 0.5-1h; then heat it to 160-180°C, and keep it warm for 0.5-1h; then heat it to 200-220°C, and keep it warm for 0.5-1h; then heat it to 250-270°C, and keep it warm for 0.5-1h; then heat it to 290-320°C, and keep it warm for 0.5-1h. ; Step seven is to wind the polyimide film through a winder, conduct online inspection through a slitting machine, slit it as required, and finally pack it for storage.

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

[0047] Embodiment 3:

[0048] The present embodiment provides a method for preparing a large-volume low-dielectric polyimide film, comprising the following steps: step 1, preparing and purifying compound I; step 2, dissolving compound I and other diamines in a solution, wherein other diamines are selected from TFDB and PDA, and the solvent is N,N-dimethylacetamide; step 3, after compound I and other diamines are completely dissolved, dianhydride monomers are added in batches, wherein dianhydrides are selected from BPDA and PMDA, the reaction temperature is controlled at 0-10° C., the reaction time is 6-24 hours, and a uniform and viscous polyamic acid solution with a certain solid content is obtained, and the resin viscosity is controlled at 100-250 Pa·s; step 4, placing the mixed polyamic acid resin in an oven, and applying vacuum for defoaming treatment, wherein the specific defoaming time is 12 hours; step 5 The defoamed polyamic acid resin is pressed into the die through a pipeline, and the thickness of the die is adjusted to make the resin evenly flow onto the mirror steel belt. The temperature of the flow box is controlled at 150±10°C, the flow speed is 5m / min, and the wind speed is controlled to evaporate most of the solvent to obtain a self-supporting film with uniform thickness; step six is ​​to pull and press the self-supporting film after the flow into a clamping plate, enter the imidization furnace, heat it from room temperature to 60-80°C, and keep it warm for 0.5-1h; then heat it to 100-130°C, and keep it warm for 0.5-1h; then heat it to 160-180°C, and keep it warm for 0.5-1h; then heat it to 200-220°C, and keep it warm for 0.5-1h; then heat it to 250-270°C, and keep it warm for 0.5-1h; then heat it to 290-320°C, and keep it warm for 0.5-1h. ; Step seven is to wind the polyimide film through a winder, conduct online inspection through a slitting machine, slit it as required, and finally pack it for storage.

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

[0050] Comparative Example 1

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

[0052] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, 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 above shows and describes the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A diamine compound I, characterized in that: The structural formula of the diamine compound I is as follows:

2. A method for preparing a diamine compound I, characterized in that: The preparation method comprises the following steps: S1. Add 4-bromoanthrone and 4-trifluoromethylphenylboric acid into a flask and mix them, add THF for dissolution reaction; then add K2CO3 aqueous solution and methyltrioctylammonium chloride, and stir the mixture under argon atmosphere at room temperature; then add tetrakistriphenylphosphine palladium as a catalyst, and stir the reaction mixture at 344K; after cooling to room temperature, concentrate the product and purify it by silica gel column chromatography; S2, adding 2-bromo-1-bromomethyl-4-ethylbenzene and triethyl phosphite into a flask for mixing, and stirring at 423K under an argon atmosphere; then cooling the mixture to room temperature, adding the compound obtained after purification in step 1, THF and potassium tert-butoxide, and stirring the reaction mixture at room temperature; after the reaction, concentrating the product, and purifying it by silica gel column chromatography; S3, adding the compound obtained after purification in step 2 and 4-aminophenylboronic acid into a flask for mixing, adding THF for dissolution reaction; adding K2CO3 aqueous solution and methyltrioctylammonium chloride, stirring the mixture at room temperature under argon atmosphere; then adding tetrakistriphenylphosphine palladium as a catalyst, and stirring the reaction mixture at 344K; after cooling to room temperature, concentrating the product, and purifying it by silica gel column chromatography; S4, adding the compound obtained after purification in step 3, p-fluoronitrobenzene and cesium fluoride into a flask for mixing, adding DMSO for dissolution reaction; stirring under argon atmosphere at 423K, cooling to room temperature, concentrating the product, and purifying it by silica gel column chromatography; S5. Add the compound obtained after purification in step 4, 10% Pd / C catalyst, and hydrazine monohydrate into a flask for mixing, add ethanol for dissolution reaction, stir at 354K under argon atmosphere, and then filter the mixture to remove the Pd / C catalyst; after the mixture is cooled to room temperature, separate the precipitated crystals by filtration, recrystallize twice with ethanol, grind into powder, and dry under vacuum to finally obtain compound I.

3. The method for preparing a diamine compound I according to claim 2, characterized in that: The molar ratio of 4-bromoanthrone, 4-trifluoromethylbenzeneboronic 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.

4. A method for preparing a large-volume low-dielectric polyimide film, characterized in that: The preparation method comprises the following steps: Step 1, preparing and purifying compound I according to the method described in claim 2; Step 2, dissolving compound I and diamine monomer in an organic solvent; Step 3: After the compound I and the diamine monomer are completely dissolved, a dianhydride monomer is added to react to obtain a polyamic acid resin solution; Step 4: placing the mixed polyamic acid resin solution in a vacuum oven for defoaming; Step 5, the defoamed polyamic acid resin solution is flowed through a die head onto a mirror steel belt to form a self-supporting film; Step 6: The self-supporting film is subjected to imidization treatment by longitudinal and transverse imidization in an imidization furnace to obtain a polyimide film; Step 7: The polyimide film is rolled up by a winder, inspected online by a slitting machine, slit as required, and finally packaged and put into storage.

5. The method for preparing 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 ratio of the sum of the mass of the diamine monomer and the dianhydride monomer to the mass of the organic solvent is (1.5-2.5):

10.

6. The method for preparing 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 method for preparing 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 for preparing a super-large volume low dielectric polyimide film according to claim 4, characterized in that: The diamine monomer is one of RODA, TFDB and PDA.

9. Application of the ultra-large volume low dielectric polyimide film obtained by the method for preparing an ultra-large volume low dielectric polyimide film according to any one of claims 4 to 8 in the field of communications.

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