Polyarylether resin with side group containing quinoxaline structure as well as preparation method and application of polyarylether resin

Abstract

The invention discloses polyarylether resin with a side group containing a quinoxaline structure as well as a preparation method and application of the polyarylether resin. The polyarylether resin with the side group containing the quinoxaline structure has a structure as shown in a formula I, the polyarylether resin provided by the invention is a novel polyarylether structural material, has relatively high heat resistance, can be dissolved in various organic solvents due to the lateral group action, and is beneficial to solution-method processing and forming of the material.

Description

Technical Field

[0001] This application relates to a polyarylene ether resin with a quinoxaline-containing side group, its preparation method, and its application, belonging to the field of polymer synthesis technology. Background Technology

[0002] Polyaryl ether resins are a class of high-performance specialty engineering plastics. Due to their unique structural characteristics, they possess excellent thermal stability, mechanical properties, and dimensional stability, making them widely applicable in the automotive, microelectronics, precision instrument, and aerospace industries. Amorphous polyaryl ether resins, as a type of polyaryl ether resin, exhibit excellent heat resistance and dimensional stability. However, traditional polyaryl ether resins either have insufficient heat resistance or limited processability, which restricts their application as high-performance polymers. To address these issues, heteroatoms such as nitrogen and phosphorus are introduced into carbon, hydrogen, and oxygen-based polymers. This improves the material's heat resistance while providing larger side groups, reducing molecular chain stacking, and facilitating solution processing.

[0003] CN1098097A discloses a novel high-temperature resistant soluble polyaryletherketone resin and its preparation method. By introducing bisphenols containing a diazanaphthalene structure, the chain rigidity of the resin is improved, internal rotation is restricted, and the heat resistance of the polymer is improved while maintaining the amorphous structure.

[0004] CN102660016A discloses a terpolymer of 2,6-dihalobenzonitrile-4,4′-dihalobenzophenone-phenolphthalein and its preparation method. The nitrile group is introduced on the dihalo side group, which improves the heat resistance and has good solubility and processing characteristics. The intrinsic viscosity is ≥0.2dL / g, the glass transition temperature is 225℃~265℃, the initial weight loss temperature is 340℃~385℃, and the temperature at which the weight loss is 5% is 400℃~490℃.

[0005] CN103554478A discloses a phosphorus-containing polyarylether ketone and its preparation method. The number-average molecular weight of the phosphorus-containing polyarylether ketone is 30,000 to 150,000, and the Tg can reach above 250℃. Due to the retention of the phenolphthalein side group, the solubility is enhanced. Summary of the Invention

[0006] This application introduces a bulky, rigid quinoxaline structure into the polymer backbone. This bulky, rigid quinoxaline structure restricts the movement of the polymer molecular chains, resulting in a polymer with a high glass transition temperature. Furthermore, the introduction of the bulky quinoxaline structure increases the free volume of the polymer, improving its solubility and enabling its application in specialty engineering plastics.

[0007] By introducing nitrogen and phosphorus atoms, the rigidity of the polymer backbone is strengthened, and the glass transition temperature (Tg) increases. To further improve the internal rotational energy barrier of the polymer chain, an ortho-substituted benzene ring structure is introduced into the polymer. At the same time, a halogen is designed to be placed at the para position of the benzene ring. The electron-withdrawing properties of quinoxaline can activate the para-halogen, successfully introducing the quinoxaline structure into polyaryl ether resin. The rigid, large-volume quinoxaline structure gives polyaryl ethers extremely high heat resistance, with a glass transition temperature reaching up to 300℃.

[0008] According to one aspect of this application, a polyarylene ether resin with a quinoxaline-containing side group structure is provided, the polyarylene ether resin having the structure shown in Formula I;

[0009]

[0010] In Formula I, R1, R2, R3, and R4 are independently selected from one of hydrogen, fluorine, methyl, isopropyl, trifluoromethyl, phenyl, and cyano.

[0011] Ar is derived from one of phenolphthalein, bisphenol A, hexafluorobisphenol A, bisphenol fluorene, phenolphthalein, o-cresolphthalein, thymolphthalein, and 3,3-bis(4-hydroxyphenyl)-2-phenylisoindoline-1-one;

[0012] The value of n ranges from 2 to 200.

[0013] Optionally, the polyaryl ether resin with a quinoxaline side group is selected from one of the structures shown in Formula I-1, Formula I-2, Formula I-3, Formula I-4, Formula I-5, Formula I-6, Formula I-7, and Formula I-8.

[0014]

[0015]

[0016] Optionally, the glass transition temperature of the polyaryletherketone is 210–300°C.

[0017] Optionally, the glass transition temperature of the polyaryletherketone is independently selected from any value of 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, or a range between any two of the above.

[0018] According to another aspect of this application, a method for preparing the above-described polyaryl ether resin with a quinoxaline-containing side group is provided, the method comprising:

[0019] Under an inactive atmosphere, a mixture containing phenolphthalein compounds, dihalogen compounds with quinoxaline structures, a catalyst, a dehydrating agent, and a solvent is reacted to obtain the polyaryl ether resin with quinoxaline side groups.

[0020] Optionally, the phenolphthalein compound is selected from phenolphthalein, bisphenol A, hexafluorobisphenol A, bisphenol fluorene, phenolphthalein, o-cresolphthalein, thymolphthalein, and 3,3-bis(4-hydroxyphenyl)-2-phenylisoindoline-1-one.

[0021] Optionally, the dihalogenated compound containing a quinoxaline structure is selected from at least one of 2,3-bis(4-fluorophenyl)quinoxaline, 2,3-bis(4-fluorophenyl)-6-methylquinoxaline, 2,3-bis(4-fluorophenyl)-6-methoxyquinoxaline, 2,3-bis(4-fluorophenyl)-6-trifluoromethoxyquinoxaline, 2,3-bis(4-fluorophenyl)-6-trifluoromethylquinoxaline, 2,3-bis(4-chlorophenyl)-6-cyanoquinoxaline, 2,3-bis(4-chlorophenyl)-6,7-bismethylquinoxaline, 6,7-bisfluoro-2,3-bis(4-fluorophenyl)quinoxaline, and 2,3-bis(4-fluorophenyl)benzoquinoxaline.

[0022] Optionally, the molar ratio of the phenolphthalein compound to the dihalogenated compound containing the quinoxaline structure is 1:0.90 to 1:1.20.

[0023] Optionally, the molar ratio of the phenolphthalein compound to the dihalogenated compound containing the quinoxaline structure is independently selected from any value of 1:0.90, 1:1, 1:1.10, 1:1.20 or a range between any two of the above.

[0024] Optionally, the catalyst is selected from at least one of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, and cesium fluoride.

[0025] Optionally, the molar ratio of the phenolphthalein compound to the catalyst is 1:1 to 1:1.8.

[0026] Optionally, the molar ratio of the phenolphthalein compound to the catalyst is independently selected from any value of 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.8 or a range between any two of the above.

[0027] Optionally, the dehydrating agent is selected from at least one of toluene, xylene, trimethylbenzene, and C5-C8 alkanes.

[0028] Optionally, the dehydrating agent is selected from at least one of toluene, xylene, polymethyl substituted benzene, n-hexane, and cyclohexane.

[0029] Optionally, the molar volume ratio of the phenolphthalein compound to the dehydrating agent is 1 mmol: 5-25 mL.

[0030] Optionally, the molar volume ratio of the phenolphthalein compound to the dehydrating agent is independently selected from any value of 1 mmol: 5 mL, 1 mmol: 10 mL, 1 mmol: 15 mL, 1 mmol: 20 mL, 1 mmol: 25 mL, or a range between any two of the above.

[0031] Optionally, the solvent is selected from at least one of N-methylpyrrolidone, sulfolane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide.

[0032] Optionally, the mass ratio of the polyarylene ether resin containing the quinoxaline structure to the solvent is 15-45%.

[0033] Optionally, the reaction temperature is 160–220°C, and the reaction time is 1–10 h.

[0034] Optionally, the temperature of the reaction is independently selected from any value of 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, or a range between any two of the above.

[0035] Optionally, the reaction time is independently selected from any value of 1h, 2h, 4h, 5h, 6h, 8h, 10h or a range between any two of the above.

[0036] Optionally, the inactive atmosphere is selected from at least one of nitrogen, argon, and helium.

[0037] According to another aspect of this application, an application of the above-described polyarylether resin with a quinoxaline-containing side group structure is provided in specialty engineering plastics.

[0038] In this application, starting from the molecular design of polyarylether resin, polyarylether materials with high heat resistance and mechanical properties are prepared by polycondensation reaction of dihalogen monomers and bisphenol monomers with quinoxaline structure in the main chain.

[0039] This application discloses a type of polyaryl ether resin with a quinoxaline-containing side group and its preparation method. Introducing a quinoxaline aromatic ring into the polyaryl ether resin structure significantly increases the chain rigidity of the main chain, thereby improving the glass transition temperature and heat resistance of the material. The preparation method includes: under an inert atmosphere, reacting a mixture of a bisphenol compound, a dihalogen compound containing a quinoxaline structure, a catalyst, a dehydrating agent, and a solvent via a nucleophilic substitution reaction to obtain the polyaryl ether resin containing the quinoxaline structure. The polyaryl ether resin provided in this application is a novel polyaryl ether structural material with high heat resistance. Furthermore, the side group effect allows it to dissolve in a variety of organic solvents, which is beneficial for solution processing and molding.

[0040] The beneficial effects that this application can produce include:

[0041] This application provides a quinoxaline-structured polyaryl ether resin with large-volume side groups. By introducing quinoxaline, the glass transition temperature of the polyaryl ether resin can be increased from 170℃ to 300℃, while still maintaining good solubility and processing characteristics. This provides a reference method for the design and synthesis of polyaryl ether resins with higher temperature resistance. Attached Figure Description

[0042] Figure 1 This is a DSC diagram of the polyarylether resin containing a quinoxaline structure prepared in Example 2 of this application.

[0043] Figure 2 The 1H NMR spectrum of the polyarylene ether resin containing a quinoxaline structure prepared in Example 2 of this application.

[0044] Figure 3 This study investigates the solubility of the quinoxaline-containing polyarylether resin prepared in Example 2 of this application. 0.1 g of the polymer from Example 2 was dissolved in 1 mL of DMAc solvent and allowed to dissolve for 12 hours at room temperature. Detailed Implementation

[0045] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0046] Unless otherwise specified, all raw materials used in the embodiments of this application were purchased through commercial channels.

[0047] In this application, nuclear magnetic resonance (NMR) spectroscopy was used to measure the NMR spectrum on a JNM-ECZL400S 400MHz spectrometer, using deuterated chloroform as the solvent. The glass transition temperature (Tg) was measured using differential scanning calorimetry (DSC 25, TA). The testing procedure was as follows: under nitrogen atmosphere, the sample was heated from 30°C to 350°C, then cooled to 30°C, and then heated to 350°C again for measurement, undergoing three cycles. The cooling and heating rates were both 10°C / min. -1 .

[0048] In the embodiments of this application, "isoindolinone bisphenol" is "3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one".

[0049] Example 1

[0050] Add 3.1832 g phenolphthalein, 3.1833 g 2,3-bis(4-fluorophenyl)quinoxaline, and 1.5893 g anhydrous potassium carbonate to a three-necked flask. Add 17.60 g sulfolane as a solvent to the three-necked flask. Heat to 160 °C under nitrogen protection, adding 25 ml of xylene (containing water) for 2 hours. Increase the temperature to 220 °C and react for 8 hours.

[0051] The product was poured into a mixture of alcohol and water to precipitate, then crushed, purified, filtered, and vacuum dried to obtain a yellow polymer powder. The value of n is 50.

[0052] The glass transition temperature was determined by differential scanning calorimetry and instrumentation (DSC25, TA).

[0053] The glass transition temperature is 265℃, the tensile strength is 47.3MPa, and the elongation at break is 2.1%.

[0054]

[0055] Example 2

[0056] 3.9342 g of isoindololinone bisphenol, 3.3235 g of 2,3-bis(4-fluorophenyl)-6-methylquinoxaline, and 1.5893 g of anhydrous potassium carbonate were added to a three-necked flask. 20.57 g of sulfolane was added as a solvent to the flask. The mixture was heated to 160 °C under nitrogen protection, with 25 ml of xylene (containing water) added for 2 hours. The temperature was then increased to 210 °C, and the reaction was allowed to proceed for 10 hours.

[0057] The product was precipitated in a mixture of alcohol and water, pulverized, purified, filtered, and vacuum dried to obtain a yellow polymer powder. The value of n was 50, the glass transition temperature was 275℃, the tensile strength was 31.9 MPa, and the elongation at break was 1.7%. Figure 1 and 2 As shown, from Figure 1 It can be seen from this that the obtained polymer has excellent heat resistance. Figure 2 It can be seen from this that the polyarylether with the target structure was obtained.

[0058]

[0059] Example 3

[0060] Add 3.1832 g phenolphthalein, 3.3235 g 2,3-bis(4-fluorophenyl)-6-methylquinoxaline, and 1.5893 g anhydrous potassium carbonate to a three-necked flask. Add 18.32 g sulfolane as a solvent to the three-necked flask. Heat to 160 °C under nitrogen protection, adding 25 ml of xylene (containing water) for 2 hours. Increase the temperature to 210 °C and react for 9 hours.

[0061] The product was precipitated in a mixture of alcohol and water, pulverized, purified, filtered, and vacuum dried to obtain a yellow polymer powder. The value of n was 50, the glass transition temperature was 262℃, the tensile strength was 65 MPa, and the elongation at break was 5%.

[0062]

[0063] Example 4

[0064] 3.9342 g of isoindolone bisphenol, 3.6839 g of 2,3-bis(4-fluorophenyl)benzoquinoxaline, and 1.5893 g of anhydrous potassium carbonate were added to a three-necked flask. 21.65 g of sulfolane was added as a solvent to the flask. The mixture was heated to 160 °C under nitrogen protection, with 25 ml of xylene (containing water) added for 2 hours. The temperature was then increased to 210 °C, and the reaction was allowed to proceed for 10 hours.

[0065] The product was precipitated in a mixture of alcohol and water, pulverized, purified, filtered, and then vacuum dried to obtain a yellow polymer powder. The value of n was 50, the glass transition temperature was 300℃, the tensile strength was 48 MPa, and the elongation at break was 2.5%.

[0066]

[0067] Example 5

[0068] Add 3.3623 g of hexafluorobisphenol A, 3.1833 g of 2,3-bis(4-fluorophenyl)quinoxaline, and 1.5893 g of anhydrous potassium carbonate to a three-necked flask. Add 18.44 g of sulfolane as a solvent to the three-necked flask. Heat to 160 °C under nitrogen protection, adding 25 ml of xylene (containing water) for 2 hours. Increase the temperature to 210 °C and react for 3 hours.

[0069] The product was precipitated in a mixture of alcohol and water, pulverized, purified, filtered, and vacuum dried to obtain a yellow polymer powder. The value of n was 50, the glass transition temperature was 217℃, the tensile stress was 68.5 MPa, and the elongation at break was 3.5%.

[0070]

[0071] Example 6

[0072] 3.3623 g of hexafluorobisphenol A, 3.4638 g of 2,3-bis(4-fluorophenyl)-6,7-bis(methyl)quinoxaline, and 1.5893 g of anhydrous potassium carbonate were added to a three-necked flask. 19.28 g of sulfolane was added as a solvent to the flask. The mixture was heated to 160 °C under nitrogen protection, with 25 ml of xylene (containing water) added for 2 hours. The temperature was then increased to 210 °C, and the reaction was allowed to proceed for 6 hours.

[0073] The product was precipitated in a mixture of alcohol and water, pulverized, purified, filtered, and vacuum dried to obtain a yellow polymer powder. The value of n was 50, the glass transition temperature was 225℃, the tensile strength was 23.8 MPa, and the elongation at break was 1.5%.

[0074]

[0075] Example 7

[0076] 3.9342 g of isoindololinone bisphenol, 3.8630 g of 2,3-bis(4-fluorophenyl)-6,7-dimethylquinoxaline, and 1.5893 g of anhydrous potassium carbonate were added to a three-necked flask. 22.19 g of sulfolane was added as a solvent to the flask. The mixture was heated to 160 °C under nitrogen protection, with 25 ml of xylene (containing water) added for 2 hours. The temperature was then increased to 210 °C, and the reaction was allowed to proceed for 1 hour.

[0077] The product was precipitated in a mixture of alcohol and water, pulverized, purified, filtered, and vacuum dried to obtain a yellow polymer powder. The value of n was 50, the glass transition temperature was 273℃, the tensile strength was 37.2 MPa, and the elongation at break was 6%.

[0078]

[0079] Example 8

[0080] 3.9342 g of isoindololinone bisphenol, 3.4334 g of 2,3-bis(4-fluorophenyl)-6-acrylonitrile quinoxaline, and 1.5893 g of anhydrous potassium carbonate were added to a three-necked flask. 20.91 g of sulfolane was added as a solvent to the flask. The mixture was heated to 160 °C under nitrogen protection, with 25 ml of xylene (containing water) added for 2 hours. The temperature was then increased to 210 °C, and the reaction was allowed to proceed for 3 hours.

[0081] The product was precipitated in a mixture of alcohol and water, pulverized, purified, filtered, and vacuum dried to obtain a yellow polymer powder. The value of n was 50, the glass transition temperature was 290℃, the tensile strength was 75 MPa, and the elongation at break was 7.2%.

[0082]

[0083] Example 9

[0084] Solubility test: 0.1 g of the polymer prepared in Example 2 was dissolved in 1 mL of N,N-dimethylacetamide (DMAc) solvent and dissolved at room temperature for 12 h.

[0085] like Figure 3 As shown, from Figure 3 As can be seen, the polymer is completely dissolved in DMAc solvent at room temperature.

[0086] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A polyaryl ether resin with a quinoxaline-containing side group, characterized in that, The polyarylene ether resin with a quinoxaline-containing side group structure has the structure shown in Formula I. In Formula I, R1, R2, R3, and R4 are independently selected from one of hydrogen, fluorine, methyl, isopropyl, trifluoromethyl, phenyl, and cyano. Ar is derived from one of phenolphthalein, bisphenol A, hexafluorobisphenol A, bisphenol fluorene, phenolphthalein, o-cresolphthalein, thymolphthalein, and 3,3-bis(4-hydroxyphenyl)-2-phenylisoindoline-1-one; The value of n ranges from 2 to 200.

2. The polyaryl ether resin with a quinoxaline-containing side group according to claim 1, characterized in that, The polyaryl ether resin with a quinoxaline side group structure is selected from one of the structures shown in Formula I-1, Formula I-2, Formula I-3, Formula I-4, Formula I-5, Formula I-6, Formula I-7, and Formula I-8. Preferably, the glass transition temperature of the polyaryletherketone is 210–300°C.

3. The method for preparing the polyaryl ether resin with a quinoxaline-containing side group as described in any one of claims 1 to 2, characterized in that, The preparation method includes: Under an inactive atmosphere, a mixture containing phenolphthalein compounds, dihalogen compounds with quinoxaline structures, a catalyst, a dehydrating agent, and a solvent is reacted to obtain the polyaryl ether resin with quinoxaline side groups.

4. The preparation method according to claim 3, characterized in that, The phenolphthalein compounds are selected from one of phenolphthalein, bisphenol A, hexafluorobisphenol A, bisphenol fluorene, phenolphthalein, o-cresolphthalein, thymolphthalein, and 3,3-bis(4-hydroxyphenyl)-2-phenylisoindoline-1-one; Preferably, the dihalogenated compound containing a quinoxaline structure is selected from at least one of 2,3-bis(4-fluorophenyl)quinoxaline, 2,3-bis(4-fluorophenyl)-6-methylquinoxaline, 2,3-bis(4-fluorophenyl)-6-methoxyquinoxaline, 2,3-bis(4-fluorophenyl)-6-trifluoromethoxyquinoxaline, 2,3-bis(4-fluorophenyl)-6-trifluoromethylquinoxaline, 2,3-bis(4-chlorophenyl)-6-cyanoquinoxaline, 2,3-bis(4-chlorophenyl)-6,7-bismethylquinoxaline, 6,7-bisfluoro-2,3-bis(4-fluorophenyl)quinoxaline, and 2,3-bis(4-fluorophenyl)benzoquinoxaline. Preferably, the molar ratio of the phenolphthalein compound to the dihalogenated compound containing the quinoxaline structure is 1:0.90 to 1:1.

20.

5. The preparation method according to claim 3, characterized in that, The catalyst is selected from at least one of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium bicarbonate, and cesium fluoride. Preferably, the molar ratio of the phenolphthalein compound to the catalyst is 1:1 to 1:1.

8.

6. The preparation method according to claim 3, characterized in that, The water-removing agent is selected from at least one of toluene, xylene, trimethylbenzene, and C5-C8 alkanes; Preferably, the molar volume ratio of the phenolphthalein compound to the dehydrating agent is 1 mmol: 5-25 mL.

7. The preparation method according to claim 3, characterized in that, The solvent is selected from at least one of N-methylpyrrolidone, sulfolane, dimethyl sulfoxide, N,N-dimethylacetamide, and N,N-dimethylformamide; Preferably, the mass ratio of the polyarylene ether resin containing the quinoxaline structure to the solvent is 15-45%.

8. The preparation method according to claim 3, characterized in that, The reaction temperature is 160–220°C, and the reaction time is 1–10 h.

9. The preparation method according to claim 3, characterized in that, The inactive atmosphere is selected from at least one of nitrogen, argon, and helium.

10. The application of the polyarylene ether resin with a quinoxaline-containing side group as described in any one of claims 1 to 2 in special engineering plastics.

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