Fluorine-containing polyarylether resin and preparation method thereof

Abstract

The invention provides fluorine-containing polyarylether resin and a preparation method thereof, and belongs to the technical field of high polymer materials. The fluorine-containing polyarylether resin provided by the invention has a polyarylether skeleton structure, and the polyarylether skeleton structure endows the resin with excellent mechanical properties; the fluorine-containing substituent group is introduced, so that the resin has low dielectric loss of fluorine-containing resin, and the problems that the dielectric constant of the fluorine-containing resin is too low in a millimeter wave frequency band and the melting temperature of the fluorine-containing resin is high are solved; the average polymerization degree of the resin is limited, so that the resin has higher molecular weight, and the mechanical property of the resin is ensured. The result of the embodiment shows that the melting temperature of the fluorine-containing polyarylether resin provided by the invention is 246 DEG C, the tensile strength reaches 82MPa, the elongation at break is 134%, and the dielectric constant is 3.28 and the dielectric loss is 0.0059 at the frequency of 0.1 MHz.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a fluorine-containing polyarylene ether resin and a preparation method thereof. Background Art

[0002] As an essential component of modern materials science, polymer materials play a key role in numerous fields due to their unique physical and chemical properties. Fluoropolymers, such as polytetrafluoroethylene (PTFE), perfluoroalkoxy polymers (PFA), and fluorinated ethylene propylene copolymers (FEP), are widely used in high-frequency electronic devices, aerospace wire coating, and microelectronics packaging due to their excellent chemical stability, low dielectric constant, and low dielectric loss.

[0003] However, existing fluoropolymers have some problems in practical applications: limited by their own fatty chain segment structure, their tensile strength is low and their melting point is high. As the earliest and most widely used PTFE resin, due to the high symmetry and high crystallinity of the PTFE molecular chain, the molecular chain segments are easy to slip, resulting in poor creep resistance and easy deformation after long-term use; the melting temperature of PTFE is as high as 327°C, and the melt viscosity is extremely high. It cannot be formed by conventional melt processing (such as injection molding, extrusion), and usually relies on sintering or machining, resulting in high manufacturing costs and complex processes; although resins such as PFA and FEP can be melt-processed, their heat resistance and mechanical properties are poor (tensile strength 25-35MPa). In addition, although PTFE has extremely low dielectric loss (tanδ≈0.0002) at low frequencies (<1GHz), its dielectric constant (ε≈2.1) is too low in the millimeter wave band (>10GHz), making it difficult to meet the requirements of 5G / 6G communications for high dielectric constants (ε>2.1).

[0004] Compared with aliphatic polymers, aromatic heterocyclic polymers have advantages in mechanical properties and temperature resistance. Traditional polyarylethers, such as polyetheretherketone (PEEK), have a tensile strength exceeding 90MPa, and also have excellent corrosion resistance, wear resistance, and good processing properties. However, their dielectric loss increases significantly at high frequencies (tanδ>0.01), making them unsuitable for high-frequency and high-speed signal transmission. Summary of the Invention

[0005] The present invention provides a fluorinated polyarylene ether resin and a method for preparing the same. The fluorinated polyarylene ether resin has high tensile strength and elongation at break, excellent high-frequency dielectric constant and dielectric loss, and a low melting temperature, allowing conventional melt processing and molding.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a fluorine-containing polyarylene ether resin having a chemical structure shown in Formula I,

[0008]

[0009] In the formula I, n is the average degree of polymerization, and n is not less than 200;

[0010] In the formula I, Ar is one of the following structures:

[0011]

[0012] Preferably, the fluorine-containing polyarylene ether resin has a crystallinity of 35 to 50%.

[0013] The present invention also provides a method for preparing the fluorinated polyarylene ether resin described in the above technical solution, comprising: mixing a monomer, a catalyst, a water-carrying agent, and an organic solvent, performing a salt-forming reaction to obtain a salt-forming monomer, and then performing a polymerization reaction to obtain a fluorinated polyarylene ether resin;

[0014] The polymerization reaction temperature is 230-270°C;

[0015] The monomer is 3,4-difluorophenol, 3,4,5-trifluorophenol, 2,4,5-trifluorophenol, 2,3,4,5-tetrafluorophenol, 2,3,4,5,6-pentafluorophenol, 4-fluoro-3-trifluoromethylphenol, 4-fluoro-3,5-bis(trifluoromethyl)phenol, 4-fluoro-2,5-bis(trifluoromethyl)phenol, 4-fluoro-2,3,5-tris(trifluoromethyl)phenol, 4-fluoro-2,3,5,6-tetra(trifluoromethyl)phenol, 4'-fluoro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-phenol, 4'-fluoro-2,6,2'-tris(trifluoromethyl)[1,1'-biphenyl]-4-phenol or 4'-fluoro-2,6,2',6'-tetra(trifluoromethyl)[1,1'-biphenyl]-4-phenol.

[0016] Preferably, the catalyst is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and cesium fluoride.

[0017] Preferably, the molar ratio of metal ions to monomers in the catalyst is (1-3):1.

[0018] Preferably, the holding time of the polymerization reaction is 1 to 8 hours.

[0019] Preferably, the organic solvent is one or two of diphenyl sulfone, diphenyl ether, sulfolane, N-methylpyrrolidone, tetrahydrofuran, 1,4-diphenoxybenzene and 1,4-diphenylsulfonylbenzene.

[0020] Preferably, the mass ratio of the organic solvent to the monomer is (70-50):(30-50).

[0021] Preferably, the temperature of the salt-forming reaction is 140-170°C.

[0022] Preferably, the holding time of the salt-forming reaction is 1 to 6 hours.

[0023] The present invention provides a fluorine-containing polyarylene ether resin having a chemical structure shown in Formula I. The fluorine-containing polyarylene ether resin provided by the present invention has a polyarylene ether skeleton structure, which gives the resin excellent mechanical properties; by introducing fluorine-containing substituents into the polyarylene ether skeleton structure, the resin has the low dielectric loss of the fluorine-containing resin, and also improves the problem of the fluorine-containing resin having too low a dielectric constant in the millimeter wave frequency band and the problem of the fluorine-containing resin having a high melting temperature; by limiting the average degree of polymerization of the resin, the resin has a higher molecular weight, thereby ensuring the mechanical properties of the resin. The results of the embodiment show that the fluorine-containing polyarylene ether resin provided by the present invention has a melting temperature of 246°C, a tensile strength of 82MPa, an elongation at break of 134%, a dielectric constant of 3.28 at a frequency of 0.1MHz, and a dielectric loss of 0.0059. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is an infrared spectrum of the fluorinated polyarylene ether resin of Example 4 of the present invention;

[0025] Figure 2 This is the H-NMR spectrum of the fluorinated polyarylene ether resin of Example 4 of the present invention;

[0026] Figure 3 This is the thermogravimetric curve of the fluorinated polyarylene ether resin of Example 4 of the present invention;

[0027] Figure 4 This is a temperature-increasing differential scanning calorimetry analysis curve of the fluorinated polyarylene ether resin of Example 4 of the present invention;

[0028] Figure 5 is the XRD spectrum of the fluorinated polyarylene ether resin of Example 4 of the present invention;

[0029] Figure 6 is the stress-strain curve of the fluorinated polyarylene ether resin of Example 4 of the present invention;

[0030] Figure 7 This is the dielectric property curve of the fluorinated polyarylene ether resin of Example 4 of the present invention. DETAILED DESCRIPTION

[0031] All raw materials of the present invention are not particularly limited in their sources and can be purchased from the market or prepared according to conventional methods well known to those skilled in the art.

[0032] There is no particular limitation on the purity of all raw materials in the present invention, and analytically pure raw materials are preferably used in the present invention.

[0033] The present invention provides a fluorine-containing polyarylene ether resin having a chemical structure shown in Formula I,

[0034]

[0035] In the formula I, n is the average degree of polymerization, and n is not less than 200;

[0036] In the formula I, Ar is one of the following structures:

[0037]

[0038] As an embodiment of the present invention, the average polymerization degree n may be 200-1000, or 400-800.

[0039] In the present invention, the crystallinity of the fluorinated polyarylene ether resin is preferably 35-50%, more preferably 39-45%. Semi-crystalline polyarylene ether resin has the structural characteristics of both crystalline and amorphous regions, which is beneficial for further improving the tensile strength and elongation at break of the resin.

[0040] The fluorinated polyarylene ether resin provided by the present invention has a polyarylene ether skeleton structure, which imparts excellent mechanical properties to the resin. By introducing fluorinated substituents, the resin has the low dielectric loss of fluorinated resins and also improves the problems of too low dielectric constant and high melting temperature of fluorinated resins in the millimeter wave frequency band. By limiting the average degree of polymerization of the resin, the resin has a higher molecular weight, thereby ensuring the mechanical properties of the resin.

[0041] The present invention also provides a method for preparing the fluorinated polyarylene ether resin described in the above technical solution, comprising: mixing a monomer, a catalyst, a water-carrying agent, and an organic solvent, performing a salt-forming reaction to obtain a salt-forming monomer, and then performing a polymerization reaction to obtain a fluorinated polyarylene ether resin;

[0042] The polymerization reaction temperature is 230-270°C;

[0043] The monomer is 3,4-difluorophenol, 3,4,5-trifluorophenol, 2,4,5-trifluorophenol, 2,3,4,5-tetrafluorophenol, 2,3,4,5,6-pentafluorophenol, 4-fluoro-3-trifluoromethylphenol, 4-fluoro-3,5-bis(trifluoromethyl)phenol, 4-fluoro-2,5-bis(trifluoromethyl)phenol, 4-fluoro-2,3,5-tris(trifluoromethyl)phenol, 4-fluoro-2,3,5,6-tetra(trifluoromethyl)phenol, 4'-fluoro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-phenol, 4'-fluoro-2,6,2'-tris(trifluoromethyl)[1,1'-biphenyl]-4-phenol or 4'-fluoro-2,6,2',6'-tetra(trifluoromethyl)[1,1'-biphenyl]-4-phenol.

[0044] The invention mixes monomers, catalysts, water-carrying agents and organic solvents and then performs salt-forming reaction to obtain salt-forming monomers.

[0045] In the present invention, the monomers are 3,4-difluorophenol, 3,4,5-trifluorophenol, 2,4,5-trifluorophenol, 2,3,4,5-tetrafluorophenol, 2,3,4,5,6-pentafluorophenol, 4-fluoro-3-trifluoromethylphenol, 4-fluoro-3,5-bis(trifluoromethyl)phenol, 4-fluoro-2,5-bis(trifluoromethyl)phenol, 4-fluoro-2,3,5-trifluorophenol, (Trifluoromethyl)phenol, 4-fluoro-2,3,5,6-tetrakis(trifluoromethyl)phenol, 4'-fluoro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-phenol, 4'-fluoro-2,6,2'-tris(trifluoromethyl)[1,1'-biphenyl]-4-phenol or 4'-fluoro-2,6,2',6'-tetrakis(trifluoromethyl)[1,1'-biphenyl]-4-phenol.

[0046] In the present invention, the catalyst is preferably one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and cesium fluoride, more preferably potassium carbonate. The above-mentioned catalysts are conducive to the polymerization reaction and reduce side reactions.

[0047] In the present invention, the molar ratio of metal ions to monomers in the catalyst is preferably (1-3):1, more preferably 2:1. The metal ions in the catalyst react with the monomers to form salts. When the molar ratio of metal ions to monomers in the catalyst is within the above range, the phenolic hydroxyl group and the para-position fluorine substituent can be salified, providing sufficient nucleophilic substitution activation sites, which is beneficial for controlling the reaction rate and reducing side reactions.

[0048] In the present invention, the organic solvent is preferably one or two of diphenyl sulfone, diphenyl ether, sulfolane, N-methylpyrrolidone, tetrahydrofuran, 1,4-diphenoxybenzene, and 1,4-diphenylsulfonylbenzene. These organic solvents can dissolve and evenly disperse the monomers without affecting the reaction, thereby facilitating the reaction.

[0049] In the present invention, the mass ratio of the organic solvent to the monomer is preferably (70-50):(30-50), more preferably (70-50):30. As one embodiment of the present invention, the mass ratio of the organic solvent to the monomer may be 70:30, 60:40, or 50:50. When the mass ratio of the organic solvent to the monomer is within this range and the monomer concentration is moderate, it is beneficial to control the reaction rate and improve the overall performance of the resin.

[0050] As an embodiment of the present invention, the water-carrying agent may be xylene; and the usage ratio of the water-carrying agent to the monomer may be (1-5) mL: (1-5) g.

[0051] The present invention has no particular limitation on the mixing method, and any conventional mixing method in the art may be used.

[0052] In the present invention, the temperature of the salt-forming reaction is preferably 140-170°C, more preferably 140-160°C. As one embodiment of the present invention, the salt-forming reaction can be initiated at 140°C and carried out within a certain temperature range. A temperature within the above range facilitates sufficient reaction between the monomer and the catalyst, providing sufficient nucleophilic substitution active sites.

[0053] As an embodiment of the present invention, the heating rate for heating to the salt-forming reaction temperature may be 1°C / 5min to 10°C / min; in an embodiment of the present invention, the heating rate for heating to the salt-forming reaction temperature is 3°C / min.

[0054] In the present invention, the holding time of the salt-forming reaction is preferably 1 to 6 hours, more preferably 2 to 3 hours; the holding time of the salt-forming reaction within the above range is conducive to sufficient reaction between the monomer and the catalyst, providing sufficient nucleophilic substitution active sites.

[0055] As an embodiment of the present invention, the water generated by the salt-forming reaction and the water-carrying agent are removed in the form of an azeotrope through a Dean-Stark trap.

[0056] After obtaining the salt-forming monomer, the present invention performs a polymerization reaction to obtain a fluorine-containing polyarylene ether resin.

[0057] In the present invention, the polymerization reaction temperature is 230-270° C., preferably 240-260° C.; as an embodiment of the present invention, the polymerization reaction temperature can be 230° C., 240° C., 250° C., 260° C., or 270° C. The polymerization reaction temperature within the above range can provide sufficient energy for the polymerization reaction, promote the polymerization reaction toward the polymer direction, reduce side reactions, and increase the molecular weight of the resin.

[0058] As an embodiment of the present invention, the heating rate to the polymerization reaction temperature may be 1°C / 5min to 10°C / min; in an embodiment of the present invention, the heating rate to the polymerization reaction temperature is 5°C / min.

[0059] In the present invention, the holding time of the polymerization reaction is preferably 1 to 8 hours, more preferably 3 to 6 hours. As one embodiment of the present invention, the holding time of the polymerization reaction can be 1 hour, 2 hours, 4 hours, 5 hours, or 7 hours. When the holding time of the polymerization reaction is within the above range, the polymerization reaction can proceed sufficiently, which is beneficial for further increasing the molecular weight and tensile strength of the resin.

[0060] As an embodiment of the present invention, the degree of the polymerization reaction can be determined by observing the state of the system. As the polymerization reaction proceeds, the viscosity of the system will increase significantly. When it increases to a certain extent, the viscosity of the system will tend to stabilize. When the viscosity of the system stabilizes, the reaction can be stopped.

[0061] As an embodiment of the present invention, the fluorine-containing polyarylene ether resin is prepared in an argon atmosphere.

[0062] As an embodiment of the present invention, the fluorine-containing polyarylene ether resin can be prepared in a three-necked flask.

[0063] As an embodiment of the present invention, after the polymerization reaction is completed, the reaction solution can be poured into deionized water to generate a crude polymer precipitate, and the solid can be crushed into fine powder after filtration, and the powder can be washed and dried; the washing can be carried out in sequence using ethyl acetate, deionized water and ethanol for 3 times each; the drying temperature can be 100°C, the drying time can be 10 hours, and the drying equipment can be a vacuum drying oven.

[0064] The preparation method provided by the present invention is simple and easy to implement, and the product quality is stable, which is conducive to the preparation of high-quality fluorine-containing polyarylene ether resin.

[0065] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions of the present invention. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0066] Example 1

[0067] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 325.

[0068] The preparation method comprises the following steps: adding diphenyl sulfone (126.07 g), then adding 4-fluoro-3-trifluoromethylphenol (54.03 g, 0.3 mol), and finally adding anhydrous potassium carbonate (41.46 g, 0.3 mol) and 50 mL of xylene to a 250 mL three-necked flask continuously aerated with argon; heating the resulting solution to 140° C. at a rate of 3° C. / min, refluxing with water in the range of 140-160° C. for 2 h, removing the xylene and the water generated by the reaction as an azeotrope through a Dean-Stark trap; then heating the reaction system to 270° C. at a rate of 5° C. / min and maintaining the temperature for 1 h to carry out a polymerization reaction; pouring the reaction solution into deionized water to generate a crude polymer precipitate (strips); filtering the solid to crush it into a fine powder, washing it three times with ethyl acetate, deionized water, and ethanol, respectively, and drying it in a vacuum oven at 100° C. for 10 h to obtain a fluorinated polyarylene ether resin powder.

[0069] Example 2

[0070] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 418.

[0071] The preparation method is the same as that of Example 1, except that the polymerization temperature is 250° C. and the holding time is 2 h.

[0072] Example 3

[0073] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 200.

[0074] The preparation method is the same as that of Example 1, except that the polymerization reaction temperature is 240° C. and the holding time is 2 h.

[0075] Example 4

[0076] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 481; it is recorded as CF3PPO.

[0077] The preparation method was the same as that in Example 1, except that the polymerization temperature was 240° C., the holding time was 5 h, a 1000 mL three-necked flask was used, and the amounts of the raw materials used were: diphenyl sulfone (504.28 g), 4-fluoro-3-trifluoromethylphenol (216.12 g, 1.2 mol), anhydrous potassium carbonate (165.85 g, 1.2 mol) and 200 mL of xylene.

[0078] Example 5

[0079] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 393.

[0080] The preparation method was the same as that of Example 1, except that the polymerization temperature was 240° C., the holding time was 5 h, and anhydrous potassium carbonate (20.73 g, 0.15 mol) was used.

[0081] Example 6

[0082] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 500.

[0083] The preparation method was the same as that of Example 1, except that the polymerization temperature was 240° C., the holding time was 5 h, and anhydrous potassium carbonate (62.19 g, 0.45 mol) was used.

[0084] Example 7

[0085] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 325.

[0086] The preparation method is the same as that of Example 1, except that the polymerization reaction temperature is 240° C., the holding time is 5 h, and the amounts of the raw materials used are: diphenyl sulfone (108.06 g), 4-fluoro-3-trifluoromethylphenol (72.04 g, 0.4 mol), and anhydrous potassium carbonate (55.28 g, 0.4 mol).

[0087] Example 8

[0088] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 243.

[0089] The preparation method is the same as that of Example 1, except that the polymerization reaction temperature is 240° C., the holding time is 5 h, and the amounts of the raw materials used are: diphenyl sulfone (81.05 g), 4-fluoro-3-trifluoromethylphenol (81.05 g, 0.45 mol), and anhydrous potassium carbonate (62.19 g, 0.45 mol).

[0090] Example 9

[0091] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 481.

[0092] The preparation method is the same as that of Example 1, except that the polymerization reaction temperature is 240° C., the holding time is 5 h, and the amounts of the raw materials used are: diphenyl sulfone (121.42 g), 3,4-fluoro-difluorophenol (52.04 g, 0.4 mol), and anhydrous potassium carbonate (55.25 g, 0.4 mol).

[0093] Example 10

[0094] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 371.

[0095] The preparation method is the same as that of Example 1, except that the polymerization reaction temperature is 240° C., the holding time is 5 h, and the amounts of the raw materials used are: diphenyl sulfone (128.84 g), 2,3,4,5,6-pentafluorophenol (55.22 g, 0.3 mol), and anhydrous potassium carbonate (41.46 g, 0.3 mol).

[0096] Example 11

[0097] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 118.

[0098] The preparation method is the same as that in Example 1, except that the polymerization reaction temperature is 240° C., the holding time is 5 h, and the amounts of the raw materials used are: diphenyl sulfone (137.63 g), 4'-fluoro-2,6,2'-tris(trifluoromethyl)[1,1'-biphenyl]-4-phenol (58.98 g, 0.15 mol), and anhydrous potassium carbonate (20.73 g, 0.15 mol).

[0099] Comparative Example 1

[0100] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 20.

[0101] The preparation method is as follows: To a 250mL three-necked flask continuously purged with argon, tetrahydrofuran (118.04mL) was added, followed by 4-fluoro-3-trifluoromethylphenol (45.03g, 0.25mol), and finally anhydrous potassium carbonate (20.73g, 0.15mol) and anhydrous calcium chloride (13.87g, 0.125mol). The reaction solution was then heated to 60°C for 48 hours, and the reaction solution was poured into deionized water. The resulting crude polymer precipitate was filtered, ground into a fine powder, washed three times with deionized water and ethanol, and dried in a vacuum oven at 100°C for 10 hours to obtain a fluorinated polyarylene ether resin powder.

[0102] Comparative Example 2

[0103] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 19.

[0104] The preparation method is the same as that in Example 1, except that the polymerization reaction temperature is 220° C., the holding time is 6 h, a 500 mL three-necked flask is used, and the amounts of the raw materials are: benzophenone (226.93 g), 4-fluoro-3-trifluoromethylphenol (97.25 g, 0.54 mol), anhydrous potassium carbonate (74.63 g, 0.54 mol) and 100 mL of xylene.

[0105] Comparative Example 3

[0106] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 26.

[0107] The preparation method is the same as that of Example 1, except that the polymerization reaction temperature is 180° C., the holding time is 15 h, and the amounts of the raw materials used are: sulfolane (117.67 g), 4-fluoro-3-trifluoromethylphenol (50.43 g, 0.28 mol), anhydrous potassium carbonate (38.70 g, 0.28 mol) and 50 mL of xylene.

[0108] Comparative Example 4

[0109] A fluorinated polyarylene ether resin having a chemical structure of The structure of Ar is The average degree of polymerization n is 194.

[0110] The preparation method is the same as that of Example 1, except that the polymerization reaction temperature is 190° C., the holding time is 14 h, and the amounts of the raw materials used are: N-methylpyrrolidone (102.20 mL), 4-fluoro-3-trifluoromethylphenol (45.03 g, 0.25 mol), anhydrous potassium carbonate (34.55 g, 0.25 mol) and 50 mL of xylene.

[0111] Test Example 1

[0112] The resins of the examples and comparative examples were tested using gel permeation chromatography (GPC) to obtain the molecular weight and distribution of the resins. The results are recorded in Table 1.

[0113] Table 1 Resin GPC test record

[0114]

[0115]

[0116] As can be seen from Table 1, the resin of Example 4 has both a high molecular weight and a moderate polydispersity, and achieves the best balance between mechanical properties, processing properties and preparation economy, making it the optimal choice; Comparative Examples 3 and 4 have too low molecular weights due to the low polymerization reaction temperature; Example 1 has a wide molecular weight distribution due to the short polymerization reaction time; Example 6 has a higher catalyst dosage than Example 4, and the molecular weight and molecular weight distribution of the resin are higher than Example 4.

[0117] Test Example 2

[0118] The resin of Example 4 was tested using an infrared spectrometer to obtain an infrared spectrum, as shown in FIG. Figure 1 shown. Figure 1 Medium, 1479cm -1 and 1427cm -1 The two peaks correspond to the skeleton vibration of the benzene ring (C=C stretching vibration) or the symmetrical and asymmetrical bending vibrations of the trifluoromethyl group (-CF3); 1316 cm -1 The position is related to the stretching vibration of CO, especially the CO of phenolic hydroxyl group or the ether bond COC formed. This position is also related to the vibration of -CF3, such as the stretching vibration of CF; 1279cm -1 , 1258cm -1 , 1212cm -1 and 1186cm -1 The four peaks belong to the stretching vibration of CF; 1159cm -1 and 1116cm -1 It is still CF vibration, or it is related to the COC symmetric stretching vibration of the ether bond; 1044cm -1 This region involves the stretching vibration of CO, forming an ether bond, or the in-plane bending vibration of the benzene ring; 903 cm -1 and 838cm -1 These lower wavenumbers are generally associated with phenyl ring substitution patterns, 838 cm -1 indicates para substitution, while 903 cm -1 Corresponding to other substitution patterns, such as meta or mono substitution; the OH stretching vibration of phenolic hydroxyl groups is usually between 3200-3600 cm -1 , there is no peak in this area in the infrared spectrum, indicating that the hydroxyl group participates in the reaction (such as forming ether bonds) during the polymerization process, causing the OH peak to weaken or disappear, which also supports the occurrence of the polymerization reaction.

[0119] Test Example 3

[0120] The resin of Example 4 was tested using a nuclear magnetic resonance spectrometer to obtain a hydrogen nuclear magnetic spectrum, as shown in FIG. Figure 2 shown. Figure 2 The three distinct aromatic protons are shown at 7.48 ppm (H2), 7.29 ppm (H4), and 7.17 ppm (H5), with coupling patterns consistent with the ABC spin system of 1,2,4-trisubstituted benzene. The downshift of H5 (7.17 ppm) confirms the electron-withdrawing effect of the -CF3 group. The absence of the phenolic hydroxyl proton signal (δ ~9-10 ppm) confirms the successful polymerization reaction via nucleophilic substitution.

[0121] Test Example 4

[0122] The resin of Example 4 was tested using a thermogravimetric analyzer (GB / T 27761-2011) to obtain a thermogravimetric curve, as shown in FIG. Figure 3 As shown in the figure, the air indicates that the test is carried out in an air atmosphere. Figure 3 It can be seen that the 1% thermal weight loss temperature of the resin is 485°C, and the 5% thermal weight loss temperature is 530°C, indicating that the resin has good heat resistance.

[0123] Test Example 5

[0124] The resin of Example 4 was tested using a differential scanning calorimeter (GB / T 19466.3-2004) to obtain a temperature-increasing differential scanning calorimetry analysis curve, as shown in FIG. Figure 4 As shown. Figure 4 It can be seen that the melting temperature of the resin is 246°C and the enthalpy value is 27.85 J / mol, which means that the melting temperature of the resin is relatively low and conventional melt processing methods can be used.

[0125] Test Example 6

[0126] The resin of Example 4 was tested using an X-ray diffractometer to obtain an XRD pattern, as shown in FIG. Figure 5 shown. Figure 5 In the table, CF3PPO-300℃ hot pressing-210℃-2h means the sample obtained by hot pressing the resin powder of Example 4 at 300℃ to form a film and then heat treating it at 210℃ for 2h. Figure 4 It can be seen that the crystallinity of the resin powder in Example 4 is 39.3%, while the crystallinity of the hot-pressed film after heat treatment at 210°C for 2 hours is 40.2%. This indicates that the resin has a semi-crystalline structure and that the orderly crystal structure inside the resin increases after heat treatment.

[0127] Test Example 7

[0128] The resin powder of Example 4 was hot-pressed at 300°C to form a film, which was recorded as CF3PPO-300°C-hot pressing. A tensile test was performed according to the method of GB / T1040.1-2018 to obtain a stress-strain curve, as shown in FIG. Figure 6 As shown. Figure 6 It can be seen that the tensile strength of the resin reaches 82 MPa and the elongation at break is 134%, indicating that the resin has good tensile properties.

[0129] Test Example 8

[0130] The resin powder of Example 4 was hot pressed at 300°C to form a film, which was recorded as CF3PPO-300°C-hot pressing. The dielectric property curve was obtained by testing according to the method of GB / T1409-2006. Figure 7 As shown, Figure 7 CF3PPO-300℃-hot pressing-heat treatment at 210℃ for 2h refers to the sample obtained by heat treatment of CF3PPO-300℃-hot pressing at 210℃ for 2h; Figure 7 The arrows in the figure indicate that the curves correspond to the corresponding vertical axes. Figure 7 As can be seen, at a frequency of 0.1 MHz, the dielectric constant of the resin is 3.28 and the dielectric loss is 0.0059. After heat treatment, the dielectric constant is 4.27 and the dielectric loss is 0.0030. This shows that the resin of Example 4 has a high dielectric constant and low dielectric loss before and after heat treatment, making it possible to use this material in the field of high-speed signal transmission.

[0131] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A fluorinated polyarylene ether resin, characterized in that Having the chemical structure shown in formula I, In the formula I, n is the average degree of polymerization, and n is not less than 200; In the formula I, Ar is one of the following structures:

2. The fluorinated polyarylene ether resin according to claim 1, wherein The crystallinity of the fluorine-containing polyarylene ether resin is 35-50%.

3. The method for preparing the fluorinated polyarylene ether resin according to claim 1 or 2, characterized in that: include: The monomer, catalyst, water-carrying agent and organic solvent are mixed and subjected to salt-forming reaction to obtain salt-forming monomer, and then subjected to polymerization reaction to obtain fluorine-containing polyarylene ether resin; The polymerization reaction temperature is 230-270°C; The monomer is 3,4-difluorophenol, 3,4,5-trifluorophenol, 2,4,5-trifluorophenol, 2,3,4,5-tetrafluorophenol, 2,3,4,5,6-pentafluorophenol, 4-fluoro-3-trifluoromethylphenol, 4-fluoro-3,5-bis(trifluoromethyl)phenol, 4-fluoro-2,5-bis(trifluoromethyl)phenol, 4-fluoro-2,3,5-tris(trifluoromethyl)phenol, 4-fluoro-2,3,5,6-tetra(trifluoromethyl)phenol, 4'-fluoro-2,2'-bis(trifluoromethyl)[1,1'-biphenyl]-4-phenol, 4'-fluoro-2,6,2'-tris(trifluoromethyl)[1,1'-biphenyl]-4-phenol or 4'-fluoro-2,6,2',6'-tetra(trifluoromethyl)[1,1'-biphenyl]-4-phenol.

4. The preparation method according to claim 3, characterized in that The catalyst is one or more of potassium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate and cesium fluoride.

5. The preparation method according to claim 3 or 4, characterized in that The molar ratio of the metal ions to the monomers in the catalyst is (1-3):

1.

6. The preparation method according to claim 3, characterized in that The holding time of the polymerization reaction is 1 to 8 hours.

7. The preparation method according to claim 3, characterized in that The organic solvent is one or two of diphenyl sulfone, diphenyl ether, sulfolane, N-methylpyrrolidone, tetrahydrofuran, 1,4-diphenoxybenzene and 1,4-diphenylsulfonylbenzene.

8. The preparation method according to claim 3 or 7, characterized in that The mass ratio of the organic solvent to the monomer is (70-50):(30-50).

9. The preparation method according to claim 3, characterized in that The temperature of the salt-forming reaction is 140-170°C.

10. The preparation method according to claim 9, characterized in that The holding time of the salt-forming reaction is 1 to 6 hours.

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