Modified polyarylene ether nitrile special polymer material of active difluoronitrile monomer containing large substituted side group structure and preparation method of modified polyarylene ether nitrile special polymer material

Abstract

The invention provides a modified polyarylene ether nitrile special polymer material of an active difluoronitrile monomer containing a large substituent side group structure, and a preparation process of the active difluoronitrile monomer containing the large substituent side group comprises the following steps: respectively adding 1, 3-dibromo-5-tert-butylbenzene, 3-cyano-4-fluorophenylboronic acid and tetrakis (triphenylphosphine)-palladium into an organic solvent, adding an alkaline aqueous solution, stirring, reacting, filtering, washing, and drying to obtain the modified polyarylene ether nitrile special polymer material containing the active difluoronitrile monomer containing the large substituent side group structure. The preparation method comprises the following steps: adding 3, 5-bis (4-fluoro-3-cyanophenyl)-4-tert-butylbenzene into a reaction kettle, heating and stirring under the protection of nitrogen to react, evaporating out an organic solution, and carrying out suction filtration and recrystallization to obtain the active difluoronitrile monomer 3, 5-bis (4-fluoro-3-cyanophenyl)-4-tert-butylbenzene containing the large substituted side group structure. The corresponding preparation process of the modified polyarylene ether nitrile special polymer material comprises the following steps: respectively adding an active difluoronitrile monomer containing a large substituted side group structure, 2, 2-bis (4-hydroxyphenyl) hexafluoropropane and a basic catalyst into an organic solvent, heating, stirring and reacting for 4-8 hours to obtain a viscous polymer solution, dispersing, filtering, crushing, soaking and washing in hot water, and drying to obtain the modified polyarylene ether nitrile special polymer material. The active difluoronitrile monomer containing the large side group is convenient in synthesis and preparation process and high in yield, and the corresponding modified polyarylene ether nitrile special polymer material has low dielectric constant and excellent dissolution film-forming property and has important potential application value in the field of power electronics.

Description

Technical Field

[0001] This invention belongs to the field of special polymer materials, and specifically relates to a modified polyarylene ether nitrile special polymer material containing a highly substituted side-group active difluoronitrile monomer. Background Technology

[0002] Polyarylene ether nitrile (PAHN) is an important class of specialty polymer materials. Its molecular structure simultaneously contains a rigid benzene ring, flexible ether bonds, and highly polar nitrile groups. The rigid benzene ring structure endows the material with high heat resistance and rigidity, while the flexible ether bonds ensure excellent toughness. The highly polar nitrile groups enhance the interactions between macromolecular chains, further improving the material's thermodynamic properties. These excellent comprehensive properties make PAHN capable of being used as high-performance engineering plastics, high-performance membrane materials, and specialty composite materials in various high-tech fields such as aerospace, power electronics, and new energy vehicles. Nitrile-containing active dihalogen monomers are key monomers in the preparation of PAHN. The commercially available nitrile-containing active dihalogen monomers are mainly 2,6-dichlorobenzonitrile and 2,6-difluorobenzonitrile. However, due to the introduction of highly polar nitrile groups, the dielectric constant of PAHN polymers is relatively high (above 4.0). As the power electronics industry moves towards higher integration, there is an urgent need to reduce the dielectric constant of materials. Therefore, designing novel active dihalogen monomers with nitrile-containing structures and further reducing the dielectric constant of polyarylether nitrile polymers is of great research significance and application value. Summary of the Invention

[0003] To address the problems existing in the prior art, this invention provides a modified polyarylether nitrile specialty polymer material containing a highly substituted active difluoronitrile monomer. This monomer is conveniently synthesized and has a high yield. The polyarylether nitrile specialty polymer material prepared by polymerizing this monomer with 2,2-bis(4-hydroxyphenyl)hexafluoropropane, due to the simultaneous introduction of the large free radical tert-butyl and bis(trifluoromethyl)isopropyl structures, increases the free volume of the polymer, reduces its polarizability, significantly lowers the dielectric constant of the polyarylether nitrile, and effectively improves the solubility and film-forming properties of the polyarylether nitrile polymer. This low-dielectric-constant polyarylether nitrile specialty polymer material has significant potential application value in the field of power electronics.

[0004] To achieve the above-mentioned objectives, this invention provides a modified polyarylene ether nitrile specialty polymer material containing a highly substituted side-group active difluoronitrile monomer, comprising a structural monomer and a polyarylene ether nitrile specialty polymer material, wherein the monomer is 3,5-bis(4-fluoro-3-acrylonitrile)-4-tert-butylbenzene, and simultaneously contains highly substituted tert-butyl and dicyandiamide groups, with a melting point of 192~193℃; The chemical formula of the repeating structural unit of the polyarylene ether nitrile special polymer material is: ; The number of repeating structural units is between 50 and 100, and the structural units simultaneously contain substituted tert-butyl, hexafluoroisopropyl and bis(nitrile) structures.

[0005] A method for preparing the polymer material as described in claim 1, comprising the following steps: (1) Preparation of the structural monomer: 1,3-dibromo-5-tert-butylbenzene, 3-acrylonitrile-4-fluorophenylboronic acid and tetratriphenylphosphine palladium were added to an organic solvent, and then an alkaline aqueous solution was added. The reaction was heated and stirred under nitrogen protection until a solid precipitate appeared. The organic solution was then evaporated by a nitrogen stream. After the reaction system was cooled, it was filtered and recrystallized to obtain the active difluoronitrile monomer 3,5-di(4-fluoro-3-acrylonitrile)-4-tert-butylbenzene with a large substituted side group structure. (2) Preparation of polymeric material: The active difluoronitrile monomers 3,5-bis(4-fluoro-3-acrylonitrilephenyl)-4-tert-butylbenzene, 2,2-bis(4-hydroxyphenyl)hexafluoropropane and alkaline catalyst described in step 1 are added to an organic solvent and heated and stirred for 4 to 8 hours to obtain a viscous polymer solution. The product is then dispersed in water, further filtered and pulverized, washed three times with hot water, and dried to obtain the polymeric material.

[0006] Furthermore, the molar ratio of the two reaction reagents, 1,3-dibromo-5-tert-butylbenzene and 3-cyano-4-fluorophenylboronic acid, is between 1:1.9 and 1:2.1.

[0007] 4. The method for preparing the polymer material according to claim 2, wherein the amount of tetratriphenylphosphine palladium used is 0.04 to 0.1 times the total mass of the two compounds, 1,3-dibromo-5-tert-butylbenzene and 3-acrylonitrile-4-fluorophenylboronic acid.

[0008] Further, in step 1, the organic solvent is toluene or xylene, and its amount is 3 to 5 times the total mass of the two compounds 1,3-dibromo-5-tert-butylbenzene and 3-cyano-4-fluorophenylboronic acid. The alkaline aqueous solution is a 10% to 20% sodium hydroxide aqueous solution or potassium hydroxide aqueous solution, and its amount is 0.4 to 0.8 times that of the organic solvent.

[0009] Furthermore, in step 1, the heating reaction temperature is 100~100℃, and the reaction time is 6~10 hours.

[0010] Furthermore, in step 2, the molar ratio of the two reactive monomers, 3,5-bis(4-fluoro-3-acrylonitrilephenyl)-4-tert-butylbenzene and 2,2-bis(4-hydroxyphenyl)hexafluoropropane, is 1.00:1.00~1.02:1.00.

[0011] Furthermore, in step 2, the alkaline catalyst is sodium carbonate or potassium carbonate, and its amount is 1.0 to 2.0 times the molar number of 2,2-bis(4-hydroxyphenyl)hexafluoropropane monomer.

[0012] Further, in step 2, the organic solvent is one of N,N-dimethylacetamide, N,N-dimethylformamide, or N-methylpyrrolidone, and its amount is 2.5 to 3.5 times the sum of the masses of the two reaction monomers 3,5-bis(4-fluoro-3-acrylonitrilephenyl)-4-tert-butylbenzene and 2,2-bis(4-hydroxyphenyl)hexafluoropropane.

[0013] Furthermore, in step 2, the polymerization stirring reaction temperature is between 160 and 180°C.

[0014] This invention also provides a specific preparation route for active difluoronitrile monomers containing highly substituted side groups and their modified polyarylene ether nitrile special polymer materials, as shown below:

[0015] The beneficial effects of this invention are: (1) The active difluoronitrile monomer with a large substituted side group structure provided by the present invention can be prepared by one-step reaction. The synthesis and preparation process is simple, the yield is high, and it is easy to separate, which is conducive to large-scale production and application.

[0016] (2) The modified polyarylene ether nitrile special polymer material provided by the present invention contains both tert-butyl and bis(trifluoromethyl)isopropyl structures with large free radicals in the polymer molecular chain structure, which effectively increases the free volume of the polymer, reduces the polarizability of the polymer, significantly reduces the dielectric constant of polyarylene ether nitrile, and improves the solubility and film-forming properties of polyarylene ether nitrile polymer. This low dielectric constant polyarylene ether nitrile special polymer material has important potential application value in the field of power electronics. Attached Figure Description

[0017] Figure 1 This invention relates to tri(4-vinylbenzyl-N,N-dimethylmethylammonium chloride-tripropyl)amine, which simultaneously contains triquaternary ammonium salt ions and a trivinylbenzene structural monomer. 1 H NMR spectrum.

[0018] Figure 2 This is the infrared spectrum of tri(4-vinylbenzyl-N,N-dimethylmethylammonium chloride-tripropyl)amine, a monomer containing both triquaternary ammonium salt ions and trivinylbenzene structure.

[0019] Figure 3 The infrared spectrum of the modified polyarylene ether nitrile special polymer material of the present invention. Figure 4 The modified polyarylene ether nitrile special polymer material of the present invention1 H NMR spectrum.

[0020] Figure 5 This is a photograph of the appearance of the modified polyarylene ether nitrile special polymer material solution cast into a film according to the present invention.

[0021] Figure 6 This is the chemical structural formula of the monomer in the active difluoronitrile monomer containing a large substituted side group structure of the present invention. Detailed Implementation

[0022] Preferred embodiments of the present invention will now be described in more detail with reference to specific examples.

[0023] The following are the raw materials and pharmaceuticals used in the examples: 1,3-Dibromo-5-tert-butylbenzene (99% purity), 3-cyano-4-fluorophenylboronic acid (99% purity), 2,2-bis(4-hydroxyphenyl)hexafluoropropane (99%): Anaiji Chemical Reagent Co., Ltd.; Tetraphenylphosphine palladium (8%), Shaanxi Kaida Chemical Co., Ltd.; Sodium carbonate, potassium carbonate N -Methylpyrrolidone, N , N -Dimethylacetamide, N , N - Dimethylformamide, toluene.

[0024] Dielectric constant testing instruments and standards: A TH2826 LCR digital bridge analyzer (frequency range 1 kHz to 1 MHz) was used for testing, and the result was obtained using the formula: k = (C p The formula is obtained by calculating (×d) / (k0×A), where C is... p d is the capacitance of the polymer film; d is the thickness of the film; A is the effective area of ​​the film; k0 is the dielectric constant under vacuum.

[0025] The following explains steps 1 and 2 of the manufacturing method and provides different examples: Step 1: Example 1: In a 1000 mL dry three-necked flask equipped with a mechanical stirrer, water separator, condenser, and nitrogen inlet, 19.80 g (0.12 mol) of 3-cyano-4-fluorophenylboronic acid, 17.53 g (0.06 mol) of 1,3-dibromo-5-tert-butylbenzene, 2.5 g of tetra(triphenylphosphine) palladium catalyst, and 150 mL of toluene were added. Then, 100 mL of sodium hydroxide aqueous solution (10% sodium hydroxide solid content) was added, nitrogen gas was introduced, and the mixture was heated to 110 °C and stirred for 10 hours until a solid precipitate formed. The nitrogen flow was further increased to distill off the toluene. The reaction system was condensed to room temperature, the product was filtered, and... N ,N Recrystallization of the crude product from dimethylacetamide yielded 3,5-bis(4-fluoro-3-acrylonitrile)-4-tert-butylbenzene, a reactive difluoronitrile monomer with a highly substituted side group structure, in 92% yield. Figure 1 Infrared spectrum of a reactive difluoronitrile monomer containing a highly substituted side group structure, 2873-3074 cm⁻¹ -1 The absorption peak at 2232 cm⁻¹ is a characteristic absorption peak of tert-butyl. -1 The absorption peak at 1235 cm⁻¹ is a characteristic absorption peak of the nitrile group. -1 The absorption peak at 1130 cm⁻¹ is a characteristic absorption peak of ether bonds. -1 The absorption peak at that point is a characteristic absorption peak of the CF bond. 1 ¹H NMR (CDCl₃, 400MHz): 7.85–7.9 (d, 4H), 7.59 (s, 2H), 7.44 (s, 1H), 7.32 (d, 2H); See appendix for details of each proton absorption peak in the NMR spectrum. Figure 1 The attribution within.

[0026] Example 2: In a 1000 mL dry three-necked flask equipped with a mechanical stirrer, a water separator, a condenser, and a nitrogen inlet, 18.80 g (0.114 mol) of 3-cyano-4-fluorophenylboronic acid, 17.53 g (0.06 mol) of 1,3-dibromo-5-tert-butylbenzene, 1.5 g of tetrakis(triphenylphosphine)-palladium catalyst, and 110 mL of toluene were added. Then, 45 mL of sodium hydroxide aqueous solution (20% sodium hydroxide solid content) was added, nitrogen gas was introduced, and the mixture was heated to 130 °C and stirred for 6 hours until a solid precipitate appeared. The nitrogen flow was further increased to distill off the toluene. The reaction system was condensed to room temperature, the product was filtered, and the crude product was recrystallized with N,N-dimethylacetamide to obtain the active difluoronitrile monomer 3,5-bis(4-fluoro-3-cyanophenyl)-4-tert-butylbenzene with a large substituted side group structure, with a yield of 90%.

[0027] Example 3 In a 1000 mL dry three-necked flask equipped with a mechanical stirrer, a water separator, a condenser, and a nitrogen inlet, 20.78 g (0.126 mol) of 3-cyano-4-fluorophenylboronic acid, 17.53 g (0.06 mol) of 1,3-dibromo-5-tert-butylbenzene, 3.8 g of tetrakis(triphenylphosphine)-palladium catalyst, and 190 mL of toluene were added. Then, 150 mL of sodium hydroxide aqueous solution (10% sodium hydroxide solid content) was added, nitrogen gas was introduced, and the mixture was heated to 100 °C and stirred for 10 hours until a solid precipitate appeared. The nitrogen flow was further increased to distill off the toluene. The reaction system was condensed to room temperature, the product was filtered, and the crude product was recrystallized with N,N-dimethylacetamide to obtain the active difluoronitrile monomer 3,5-bis(4-fluoro-3-cyanophenyl)-4-tert-butylbenzene with a large substituted side group structure, with a yield of 91%.

[0028] Step 2 Example 1: In a 100 mL dry three-necked flask equipped with a mechanical stirrer, a water separator, and a condenser, 7.5227 g (0.0202 mol) of the active difluoromonomer 3,5-bis(4-fluoro-3-acrylonitrile)-4-tert-butylbenzene, 6.7246 g (0.02 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane / disulfone (4-hydroxy-3,5-xylyl), and 3.18 g (0.03 mol) of sodium carbonate were added, followed by 42 mL of N-methylpyrrolidone. The reaction system was stirred at 170 °C for 8 hours to obtain a viscous polymer solution. The reaction was then terminated, and the polymer solution was dispersed in water to obtain a fibrous polymer. Further filtration, pulverization, washing three times with hot water, and drying yielded a low-dielectric-constant polyarylene ether nitrile specialty polymer material with a yield of 99%. Figure 3 Infrared spectrum of modified polyarylether nitrile specialty polymer material, 2962 cm⁻¹ -1 The broad absorption peak at 2230 cm⁻¹ is a characteristic absorption peak of tert-butyl. -1 The absorption peak at 1249 cm⁻¹ is a characteristic absorption peak of the nitrile group. -1 The absorption peak at 1170 cm⁻¹ is a characteristic absorption peak of ether bonds. -1 The absorption peak at that point is a characteristic absorption peak of the CF bond. 1 ¹H NMR (CDCl₃, 400MHz): 7.91 (s, 2H), 7.80 (d, 2H), 7.46 (m, 5H), 7.16 (m, 6H); See appendix for details of each proton absorption peak in the NMR spectrum. Figure 4 The attribution within. (Appendix) Figure 5The image shows the appearance of the film cast from the polyarylether nitrile polymer. The dielectric constant of the film was tested and found to be 2.8 at 1 MHz, which is significantly lower than the dielectric constant of commercial polyarylether nitrile materials (4.0).

[0029] Example 2: In a 100 mL dry three-necked flask equipped with a mechanical stirrer, a water separator, and a condenser, add 7.4482 g (0.02 mol) of the active difluoro monomer 3,5-bis(4-fluoro-3-acrylonitrile)-4-tert-butylbenzene, 6.7246 g (0.02 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane / disulfone (4-hydroxy-3,5-xylyl), and 2.12 g (0.02 mol) of sodium carbonate, then add 37 mL of [unspecified liquid]. N , N Dimethylacetamide was used to stir the reaction system at 160°C for 10 hours to obtain a viscous polymer solution. After the reaction was stopped, the polymer solution was poured into water to disperse and obtain a fibrous polymer. The polymer was further filtered, crushed, washed three times with hot water, and dried to obtain a special polymer material with a low dielectric constant polyarylene ether nitrile with a yield of 96%.

[0030] Example 3: In a 100 mL dry three-necked flask equipped with a mechanical stirrer, a water separator, and a condenser, add 7.5972 g (0.0204 mol) of the active difluoro monomer 3,5-bis(4-fluoro-3-acrylonitrile)-4-tert-butylbenzene, 6.7246 g (0.02 mol) of 2,2-bis(4-hydroxyphenyl)hexafluoropropane / disulfone (4-hydroxy-3,5-xylyl), and 4.24 g (0.04 mol) of sodium carbonate, then add 48 mL of [unspecified liquid]. N 1-Methylpyrrolidone was reacted by stirring the reaction system at 180°C for 6 hours to obtain a viscous polymer solution. After the reaction was stopped, the polymer solution was poured into water and dispersed to obtain a fibrous polymer. The polymer was further filtered, crushed, washed three times with hot water, and dried to obtain a special polymer material with a low dielectric constant polyarylene ether nitrile with a yield of 98%.

[0031] The above-described embodiments are merely preferred embodiments provided to fully illustrate the present invention, and the scope of protection of the present invention is not limited thereto. Equivalent substitutions or modifications made by those skilled in the art based on the present invention are all within the scope of protection of the present invention. The scope of protection of the present invention is defined by the claims.

Claims

1. A modified polyarylene ether nitrile specialty polymer material containing a highly substituted side-group active difluoronitrile monomer, characterized in that: The application relates to a special polymer material of polyarylether nitrile, which comprises a structural monomer and a special polymer material of polyarylether nitrile, wherein the monomer is 3,5-di(4-fluoro-3-nitrile phenyl)-4-tert-butyl benzene, the monomer contains a large-substituted tert-butyl group and a double nitrile group, and the melting point is 192-193 DEG C. The chemical formula of the repeating structural unit of the special polymer material of polyarylether nitrile is as follows: ； The repeating structural unit is between 50 and 100, the structural unit contains a large-substituted tert-butyl group, a hexafluoroisopropyl group and a double nitrile group.

2. A method for producing a high molecular material as claimed in claim 1, characterized in that, The application further relates to a preparation method of the special polymer material of polyarylether nitrile, which comprises the following steps: (1) preparation of a structural monomer: 1,3-dibromo-5-tert-butyl benzene, 3-nitrile-4-fluorobenzene boronic acid and tetraphenylphosphonium palladium are respectively added into an organic solvent, an alkaline aqueous solution is added, the reaction is stirred and heated under nitrogen protection, solid precipitates are generated, the organic solution is further evaporated through a nitrogen flow, the reaction system is cooled, and then is filtered and recrystallized, so that the active double-fluorine nitrile monomer 3,5-di(4-fluoro-3-nitrile phenyl)-4-tert-butyl benzene containing a large-substituted side group structure is obtained; (2) preparation of a high molecular material: the active double-fluorine nitrile monomer 3,5-di(4-fluoro-3-nitrile phenyl)-4-tert-butyl benzene containing a large-substituted side group structure in step 1, 2,2-bis(4-hydroxyphenyl) hexafluoropropane and an alkaline catalyst are respectively added into an organic solvent, the polymer solution is obtained after the reaction is stirred and heated for 4-8 hours, the product is poured into water for dispersion, and then is further filtered, crushed, washed with hot water for three times and dried, so that the high molecular material is obtained. The preparation route is as follows: 。 3. The method for preparing the polymer material according to claim 2, characterized in that, The mass ratio of the two reaction reagents, namely 1,3-dibromo-5-tert-butyl benzene and 3-nitrile-4-fluorobenzene boronic acid, is between 1:1.9 and 1:2.

1.

4. The method for preparing the polymer material according to claim 2, characterized in that, The amount of tetraphenylphosphonium palladium is 0.04-0.1 times the total mass of the two compounds, namely 1,3-dibromo-5-tert-butyl benzene and 3-nitrile-4-fluorobenzene boronic acid.

5. The method for preparing the polymer material according to claim 2, characterized in that, In step 1, the organic solvent is toluene or xylene, the amount of the organic solvent is 3-5 times the total mass of the two compounds, namely 1,3-dibromo-5-tert-butyl benzene and 3-nitrile-4-fluorobenzene boronic acid, the alkaline aqueous solution is a 10%-20% sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution, and the amount of the alkaline aqueous solution is 0.4-0.8 times the amount of the organic solvent.

6. The method for preparing the polymer material according to claim 2, characterized in that, In step 1, the heating reaction temperature is 100-100 DEG C, and the reaction time is 6-10 hours.

7. The method for preparing the polymer material according to claim 2, characterized in that, In step 2, the molar ratio of the two reaction monomers, namely 3,5-di(4-fluoro-3-nitrile phenyl)-4-tert-butyl benzene and 2,2-bis(4-hydroxyphenyl) hexafluoropropane, is 1.00:1.00-1.02:1.

00.

8. The method for preparing the polymer material according to claim 2, characterized in that, In step 2, the alkaline catalyst is sodium carbonate or potassium carbonate, and the amount of the alkaline catalyst is 1.0-2.0 times the molar number of 2,2-bis(4-hydroxyphenyl) hexafluoropropane.

9. The method for preparing the polymer material according to claim 2, characterized in that, In step 2, the organic solvent is one of N,N-dimethylacetamide, N,N-dimethylformamide and N-methyl pyrrolidone, and the amount of the organic solvent is 2.5-3.5 times the mass of the two reaction monomers, namely 3,5-di(4-fluoro-3-nitrile phenyl)-4-tert-butyl benzene and 2,2-bis(4-hydroxyphenyl) hexafluoropropane.

10. The method for preparing the polymer material according to claim 2, characterized in that, In the step 2, the polymerization stirring reaction temperature is between 160 and 180℃.

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