A preparation method of polyarylethernitrile material and its application in intrinsic ultra-low dielectric material

Abstract

The present application discloses a non-fluorine polyaryletherketone (nitrile) resin, which adjusts the size and position of the long-chain side groups through the main chain structure design, further reduces the close stacking between the molecular chains, and can form a larger pore structure during the molding process, so that it has a lower dielectric constant and dielectric loss. At the same time, the material does not produce toxic and harmful substances such as fluorophosgene when treated at high temperatures, ensuring the safety of the material. The non-fluorine low-dielectric polyaryletherketone (nitrile) resin of the present application has the advantages of low dielectric constant and low dielectric loss, and is widely used in 5G and higher frequency communication fields.

Description

Technical Field

[0001] The present technology relates to an intrinsic low-dielectric polyarylether nitrile resin and a preparation method thereof, and belongs to the field of polymer synthesis. Background Art

[0002] The electronics industry is in urgent need of low-dielectric films. To achieve high performance, low latency, small size, and high integration, conductor materials, especially wires, must possess high conductivity, and dielectric layers must have lower dielectric constants and dielectric losses. Currently, copper wires are the primary conductors used. While not as conductive as silver, their cost-effectiveness far exceeds that of silver, the most conductive wire. Consequently, the electronics industry has turned its attention to dielectric materials, hoping to improve the rapid response of electrical signals and the thinness of integrated circuits through low dielectric constants and dielectric losses. The development of high-performance, ultra-low dielectric materials has become a bottleneck hindering the current trend toward lighter, thinner, shorter, and smaller microelectronics. Furthermore, with the increase in high-frequency transmission rates, the development of 5G networks requires further reductions in the dielectric constant and dielectric loss of materials, placing even more stringent demands on material performance, a requirement that conventional polyimide resins are unable to meet.

[0003] It is well known that conventional poly(arylene ether) resins have a dielectric constant of 3.2-3.6 and a dielectric loss of 2-10‰. This is attributed to their low polarity and insulating properties. To reduce the dielectric constant of these materials, the common approach is to reduce their density and molecular polarity. Since the backbone of poly(arylene ether) resins is primarily composed of aromatic groups and ether bonds, their molecular polarity is relatively low, making them suitable for use as low-dielectric materials. Taking poly(arylene ether ketone) as an example, Zhao Xiaogang et al. reported a bisphenol A-based poly(arylene ether ketone) with a dielectric constant of 1.67. Two methyl side groups enhance the material's dielectric properties, but its glass transition temperature of only 155°C significantly limits its application in electronics. Using hexafluorobisphenol A as a monomer can further reduce the resin's dielectric constant (ε = 1.69 at 1 MHz). However, the price of the fluorinated bisphenol monomer is significantly higher than that of bisphenol A, contributing to the high price of this resin. Furthermore, degradation reactions caused by high temperatures can release highly toxic substances such as fluorophosgene, significantly impacting the environment.

[0004] CN201910479650.1 discloses a fluorinated polyarylethernitrile and its preparation method. The chemical structure of the low dielectric constant polyarylethernitrile contains trifluoromethyl, sulfone and aryl ether groups, and is in the form of a film. The low dielectric constant polyarylethernitrile film contains a large number of pores. The density of the low dielectric constant polyarylethernitrile is less than 0.15 g / cm 3, porosity greater than 80%, dielectric constant less than 1.5 at 1kHz, and dielectric loss less than 0.004 at 1kHz. Due to the phase inversion method used to prepare the film, the comprehensive properties of the material, especially the mechanical properties, are greatly reduced, making it unsuitable for making intrinsic low-dielectric film materials. Chinese patent 201510955134.3 discloses a low-dielectric polyaryletherketone resin with a main chain containing a cage-type silsesquioxane double-deck structure and its preparation method. 3,13-bis(2-methoxy-4-propylphenol)octaphenyl cage-type silsesquioxane is used as a raw material to react with difluoroketone monomers such as 4,4′-difluorobenzophenone, 1,4-(4-fluoro-benzoyl)-benzene or 4,4′-(4-fluoro-benzoyl)-1,1′-biphenyl to prepare a low-dielectric polyaryletherketone resin with a main chain containing a cage-type silsesquioxane double-deck structure. With the introduction of cage-type silsesquioxane, the dielectric constant is significantly reduced compared with traditional polyaryletherketone, reaching a minimum of 1.95. However, the high price of raw materials leads to high polymer costs, making it difficult to commercialize.

[0005] At present, there are not many bisphenol monomers containing phthalein side groups that can be commercialized, mainly phenolphthalein, o-cresolphthalein and thymolphthalein. Because the phthalein side groups give the polymer good solubility, they have good solubility in DMF, DMAc, etc. and are suitable for solution film formation. Summary of the Invention

[0006] This patent combines polyarylether resins with intrinsically low dielectric molecular design. Without retaining fluorine atoms, the primary goal is to address the problem of molecular chain stacking. In particular, the introduction of an asymmetric isopropyl group (-CH(CH3)2) into the bisphenol monomer increases the steric hindrance of the polymer side chain, hindering the stacking of the polymer main chain, increasing the molecular volume, and ultimately reducing the resin density. The intrinsically low dielectric polyaryletherketone (nitrile) resin prepared from this monomer is non-selective for active dihalogen monomers and can significantly improve the dielectric properties of the material.

[0007] According to one aspect of the present application, a novel structural bisphenol monomer is provided for use in the preparation of poly(arylene ether nitrile) resins. The resulting poly(arylene ether nitrile) resins have lower dielectric constants and higher heat resistance, and can be used to prepare thin films with low dielectric constants, low dielectric loss, and high-temperature resistance.

[0008] According to one aspect of the present application, a novel structural bisphenol monomer is provided for use in the preparation of poly(aryletherketone) resins. The resulting poly(aryletherketone) resins have lower dielectric constants and higher heat resistance, and can be used to prepare thin films with low dielectric constants, low dielectric loss, and high-temperature resistance.

[0009] In this application, "intrinsic ultra-low dielectric" refers to a dielectric with a low dielectric constant and low dielectric loss without being doped with other additives.

[0010] According to one aspect of the present application, a method for preparing a polymer is provided, comprising at least the following steps:

[0011] The raw materials containing bisphenol compound and dihalogen compound are mixed with carbonate, solvent and water-carrying agent, and reacted to obtain the polymer.

[0012] When the bisphenol compound is phenolphthalein containing an isopropyl group, the structure of the polyarylethernitrile is as follows:

[0013]

[0014] When the bisphenol compound is phenolphthalein containing an isopropyl group, the polyaryletherketone has the following structural formula:

[0015]

[0016] The bisphenol compound is selected from at least one of bisphenol A, hexafluorobisphenol A, phenolphthalein, thymolphthalein, o-cresolphthalein, bisphenol fluorene, biphenol, and hydroquinone containing at least one isopropyl group; the structure is as follows:

[0017]

[0018] The dihalogen compound is selected from at least one of 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 4,4-difluorobenzophenone and 1,4-di(4-fluorobenzoyl)benzene;

[0019] The carbonate is selected from at least one of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, cerium carbonate, and calcium carbonate;

[0020] The solvent is selected from at least one of sulfolane, diphenyl sulfone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N-cyclohexylpyrrolidone;

[0021] The water-carrying agent is selected from at least one of cyclohexane, n-heptane, benzene, toluene, xylene, and chlorobenzene.

[0022] The molar ratio of the bisphenol compound, the dihalogen compound and the carbonate is 1:0.95-1.10:0.95-1.50;

[0023] The mass of the solvent is 1.5 to 5 times the sum of the mass of the bisphenol compound and the dihalogen compound;

[0024] The mass of the water-carrying agent is 0.5 to 2 times the mass of the solvent.

[0025] The reaction conditions are as follows: heating to boiling of the water-carrying agent under nitrogen protection, maintaining for 1 to 5 hours, removing the water-carrying agent, and then heating to 150 to 230° C., maintaining for 0.5 to 24 hours.

[0026] According to one aspect of the present application, a poly(arylene ether nitrile) is provided, wherein the main chain is connected by ether bonds and carbonyl bonds, the side chains contain isopropyl structures, and the side chains do not contain polar groups such as carboxyl groups, hydroxyl groups, and sulfonic acid groups, and the poly(arylene ether nitrile) is prepared by the above-mentioned preparation method. The dihalogen compound is selected from at least one of 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile.

[0027] According to another aspect of the present application, a polyaryletherketone is provided, wherein the main chain is connected by an ether bond and a carbonyl bond, the side chain contains an isopropyl structure, and the side chain does not contain polar groups such as carboxyl groups, hydroxyl groups, and sulfonic acid groups, and is prepared by the above-mentioned preparation method. The dihalogen compound is selected from at least one of 4,4-difluorobenzophenone and 1,4-di(4-fluorobenzoyl)benzene.

[0028] According to one aspect of the present application, an intrinsic ultra-low dielectric material is provided, which is selected from the above-mentioned polyarylethernitrile or polyaryletherketone.

[0029] Dielectric constant ≤ 3.2;

[0030] The dielectric loss is ≤0.006, which can meet the 5G demand for low dielectric materials.

[0031] Glass transition temperature ≥170℃.

[0032] The beneficial effects of this application include:

[0033] 1) The present application provides an intrinsic low-dielectric polyaryletherketone (nitrile) resin having a low dielectric constant and low dielectric loss, and does not release toxic and harmful substances such as fluorophosgene when heated. Furthermore, the glass transition temperature of the material is adjustable, and the application range is wide.

[0034] 2) The intrinsic low-dielectric polyaryletherketone (nitrile) resin provided in this application has readily available raw materials and has certain cost advantages.

[0035] 3) The intrinsic low-dielectric poly(aryletherketone) (nitrile) resin provided in this application has dielectric performance advantages not found in non-substituted resins and can be extended to the synthesis of related poly(arylether) resins. DETAILED DESCRIPTION

[0036] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

[0037] Test method: The dielectric constant and dielectric loss parameters are tested using an impedance analyzer, and the test results at 1MHz are taken.

[0038] Preparation Example 3, Preparation of 3'-bis(2-isopropyl)phenolphthalein

[0039] 2-Isopropylphenol, phthalic anhydride, and methanesulfonic acid are mixed in a specific ratio, heated to 50-180°C for 0.5-24 hours, cooled, and diluted with toluene. A predetermined amount of a mixed solution of toluene and n-hexane is then added, stirred to thoroughly mix, and filtered to yield crude 3,3'-bis(2-isopropyl)phenolphthalein. After alkali washing, decolorization, and acid washing, pure white 3,3'-bis(2-isopropyl)phenolphthalein is obtained with a purity exceeding 98.5%. Innovation: The original reaction involved recrystallization from methanol and water, but this system had a stringent methanol-water ratio requirement and impurities were difficult to remove. This new procedure transfers methanesulfonic acid into the toluene system by using similar solubility and density differences between 3,3'-bis(2-isopropyl)phenolphthalein, the solvent, and byproducts, improving purification efficiency.

[0040] Comparative Example 1

[0041] 3.183g of phenolphthalein, 1.7202g of 2,6-dichlorobenzonitrile, and 2.07g of K2CO3 (50% excess) were added to a three-necked flask. 15ml of toluene was used as a water-dispersing agent, and 12g of sulfolane was used as a solvent. The mixture was heated to 130°C under nitrogen for 4 hours. The temperature was then raised to 200°C and the reaction was continued for 2 hours.

[0042] The product was poured into a mixture of alcohol and water to precipitate, crushed, boiled and washed repeatedly for 10 times, filtered and vacuum dried.

[0043] Dielectric constant: 3.52; dielectric loss 0.00981@1MHz.

[0044] Example 1

[0045] Add 4.205g of 3,3'-bis(2-isopropyl)phenolphthalein, 1.7202g of 2,6-dichlorobenzonitrile, and 2.07g of K2CO3 to a three-necked flask. Add 15ml of toluene as a water-dispersing agent and 12g of sulfolane as a solvent. Heat to 130°C under nitrogen and allow to dissolve for 4 hours. Then raise the temperature to 200°C and react for 2 hours.

[0046] The product was poured into a mixture of alcohol and water to precipitate, crushed, boiled and washed repeatedly for 10 times, filtered and vacuum dried.

[0047] Dielectric constant: 2.86; dielectric loss 0.00532@1MHz.

[0048]

[0049] Example 2

[0050] 4.0249g of 3,3'-bis(2-isopropyl)phenolphthalein, 1.091g of 4,4'-difluorobenzophenone, 0.8601g of 2,6-dichlorobenzonitrile, and 1.52g of K2CO3 (10% excess) were added to a three-necked flask. 10.9g of N-methylpyrrolidone and 15ml of toluene were added to the flask as solvent. The mixture was heated to 140°C under nitrogen with water for 2 hours. The temperature was then raised to 190°C and the reaction was continued for 12 hours.

[0051] The product was poured into a mixture of alcohol and water for precipitation, crushed, repeatedly boiled and washed eight times, filtered, and vacuum dried. The resulting polymer was dissolved in N,N-dimethylacetamide, cast, and dried into a film, and the dielectric properties were tested.

[0052] Dielectric constant: 2.98; dielectric loss 0.00532@1MHz.

[0053]

[0054] Wherein m=5, n=5.

[0055] Example 3

[0056] 2.0125g 3,3'-bis(2-isopropyl)phenolphthalein, 1.6812g hexafluorobisphenol A (1:1 molar ratio), 1.7202g 2,6-difluorobenzonitrile, and 1.69g K2CO3 were added to a three-necked flask. 12ml toluene and 12g N,N-dimethylformamide were added as solvent. The mixture was heated to 120°C under nitrogen with water for 4 hours. The temperature was then raised to 190°C and the reaction was continued for 12 hours.

[0057] The product was poured into a mixture of alcohol and water to precipitate, crushed, boiled and washed repeatedly for 10 times, filtered and vacuum dried.

[0058] Dielectric constant: 3.18; dielectric loss 0.00477@1MHz.

[0059]

[0060] Wherein m=5, n=5.

[0061] Comparative Example 2

[0062] 3.183g of phenolphthalein, 2.182g of 4,4'-difluorobenzophenone, and 2.073g of K2CO3 (50% excess) were added to a three-necked flask. 10ml of toluene and 15g of sulfolane were added as solvent. The mixture was heated to 130°C under nitrogen with water for 4 hours. The temperature was then raised to 200°C and the reaction was continued for 2 hours.

[0063] The product was poured into a mixture of alcohol and water to precipitate, crushed, boiled and washed repeatedly for 10 times, filtered and vacuum dried.

[0064] Dielectric constant: 3.26; dielectric loss 0.00485@1MHz.

[0065] Example 4

[0066] 4.0249g of 3,3'-bis(2-isopropyl)phenolphthalein, 2.182g of 4,4'-difluorobenzophenone, and 2.073g of K2CO3 (50% excess) were added to a three-necked flask. 10ml of toluene and 15g of sulfolane were added as solvent. The mixture was heated to 120°C under nitrogen with water for 2 hours. The temperature was then raised to 180°C and the reaction was continued for 4 hours.

[0067] The product was poured into a mixture of alcohol and water for precipitation, crushed, repeatedly boiled and washed 10 times, filtered, and vacuum dried. The resulting polymer was dissolved in N,N-dimethylacetamide, cast, and dried into a film, and the dielectric properties were tested.

[0068] Dielectric constant: 2.69; dielectric loss 0.00417@1MHz.

[0069]

[0070] Example 5

[0071] 4.0249g of 3,3'-bis(2-isopropyl)phenolphthalein, 1.091g of 4,4'-difluorobenzophenone, 0.8601g of 2,6-dichlorobenzonitrile, and 1.52g of K2CO3 (10% excess) were added to a three-necked flask. 10.9g of N-methylpyrrolidone and 15ml of toluene were added to the flask as solvent. The mixture was heated to 140°C under nitrogen with water for 2 hours. The temperature was then raised to 190°C and the reaction was continued for 12 hours.

[0072] The product was poured into a mixture of alcohol and water for precipitation, crushed, repeatedly boiled and washed eight times, filtered, and vacuum dried. The resulting polymer was dissolved in N,N-dimethylacetamide, cast, and dried into a film, and the dielectric properties were tested.

[0073] Dielectric constant: 2.98; dielectric loss 0.00532@1MHz.

[0074]

[0075] Wherein m=5, n=5.

[0076] Example 6

[0077] 2.1025g of 3,3'-bis(2-isopropyl)phenolphthalein, 1.752g of bisphenolfluorene (1:1 molar ratio), 2.182g of 4,4'-difluorobenzophenone, and 1.52g of K2CO3 (10% excess) were added to a three-necked flask. 8g of toluene and 14g of N,N-dimethylformamide were added as solvent. The mixture was heated to 140°C under nitrogen with water for 2 hours. The temperature was then raised to 190°C and the reaction was continued for 12 hours.

[0078] The product was poured into a mixture of alcohol and water for precipitation, crushed, repeatedly boiled and washed 10 times, filtered, and vacuum dried. The resulting polymer was dissolved in N,N-dimethylacetamide, cast, and dried into a film, and the dielectric properties were tested.

[0079] Dielectric constant: 3.04; dielectric loss 0.00509@1MHz.

[0080]

[0081] Wherein m=5, n=5.

[0082] Example 7

[0083] 2.1025g of 3,3'-bis(2-isopropyl)phenolphthalein, 1.6812g of hexafluorobisphenol A (1:1 molar ratio), 2.182g of 4,4'-difluorobenzophenone, and 1.52g of K2CO3 (10% excess) were added to a three-necked flask. 12ml of toluene and 12g of N,N-dimethylformamide were added as solvent. The mixture was heated to 140°C under nitrogen with water for 2 hours. The temperature was then raised to 190°C and the reaction was continued for 12 hours.

[0084] The product was poured into a mixture of alcohol and water for precipitation, crushed, repeatedly boiled and washed eight times, filtered, and vacuum dried. The resulting polymer was dissolved in N,N-dimethylacetamide, cast, and dried into a film, and the dielectric properties were tested.

[0085] Dielectric constant: 2.56; dielectric loss 0.0042@1MHz.

[0086]

[0087] Wherein m=5, n=5.

[0088] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. Application of a polymer in an intrinsic ultra-low dielectric material, characterized in that: The preparation method of the polymer comprises at least the following steps: Mixing raw materials containing bisphenol compounds and dihalogen compounds with carbonates, solvents, and water-carrying agents, and reacting them to obtain the polymer; The bisphenol compound is 3,3'-bis(2-isopropyl)phenolphthalein, a mixture of 3,3'-bis(2-isopropyl)phenolphthalein and hexafluorobisphenol A, or a mixture of 3,3'-bis(2-isopropyl)phenolphthalein and bisphenol fluorene; The dihalogen compound is selected from at least one of 2,6-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 4,4-difluorobenzophenone and 1,4-di(4-fluorobenzoyl)benzene.

2. The use according to claim 1, characterized in that The carbonate is selected from at least one of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, cerium carbonate, and calcium carbonate; The solvent is selected from at least one of sulfolane, diphenyl sulfone, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and N-cyclohexylpyrrolidone; The water-carrying agent is selected from at least one of cyclohexane, n-heptane, benzene, toluene, xylene, and chlorobenzene.

3. The use according to claim 1, characterized in that The molar ratio of the bisphenol compound, the dihalogen compound and the carbonate is 1:0.95-1.10:0.95-1.50; The mass of the solvent is 1.5 to 5 times the sum of the mass of the bisphenol compound and the dihalogen compound; The mass of the water-carrying agent is 0.5 to 2 times the mass of the solvent.

4. The use according to claim 1, characterized in that The reaction conditions are as follows: heating to boiling of the water-carrying agent under nitrogen protection, maintaining for 1-5 hours, removing the water-carrying agent, and then heating to 150-230° C., maintaining for 0.5-24 hours.

5. The use according to claim 1, characterized in that When the dihalogen compound is selected from at least one of 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile, the polymer is polyarylethernitrile.

6. The use according to claim 1, characterized in that When the dihalogen compound is selected from at least one of 4,4-difluorobenzophenone and 1,4-di(4-fluorobenzoyl)benzene, the polymer is polyaryletherketone.

7. The use according to claim 1, characterized in that Dielectric constant ≤ 3.2; Dielectric loss ≤ 0.006; Glass transition temperature ≥170℃.

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