Polyaryletherketone compound as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high polymer materials, and particularly relates to a polyaryletherketone compound as well as a preparation method and application thereof. The invention provides a polyaryletherketone compound. The polyaryletherketone compound has a structure as shown in a formula I which is described in the specification. The polyaryletherketone compound provided by the invention can remarkably inhibit thermal degradation and crosslinking of polyaryletherketone resin in a high-temperature processing process, greatly improves the melt processing stability of the polyaryletherketone resin, remarkably improves the thermal stability, processability and product appearance of the polyaryletherketone resin, is simple and convenient in process, is suitable for various polyaryletherketone resins, and has wide application prospects. The method has important industrial application value and wide market prospect.

Description

Technical Field

[0002] This invention belongs to the field of polymer materials technology, specifically relating to a polyarylether ketone compound, its preparation method, and its application. Background Technology

[0003] Polyaryletherketone resins are a class of semi-crystalline thermoplastic polymers. Due to their excellent heat resistance, high strength, abrasion resistance, mechanical properties, corrosion resistance, and biocompatibility, they are widely used in information technology, machinery, automotive, aerospace, and other fields.

[0004] Polyaryletherketones (PEEKs) include polyetheretherketones (PEEKs), polyetherketones (PEKs), and polyetherketone etherketones (PEKEKKs). PEEK has a melting point of 340°C and a processing temperature typically between 380 and 400°C, while PEK has a melting point of 370°C and a processing temperature around 400°C. Under these extreme conditions, many conventional antioxidants and heat stabilizers, due to insufficient heat resistance, are prone to decomposition, volatilization, or deactivation, thus failing to provide effective protection for the resin. Furthermore, due to structural differences, commonly used heat stabilizers are difficult to achieve uniform dispersion in the PEEK resin matrix and may precipitate due to poor compatibility with the matrix, not only reducing stabilization efficiency but also affecting the appearance of the product. Summary of the Invention

[0005] The purpose of this invention is to provide a polyaryletherketone compound, its preparation method, and its application. The polyaryletherketone compound and polyaryletherketone polymer provided by this invention have good compatibility and can significantly inhibit the thermal degradation and crosslinking of polyaryletherketone polymers during high-temperature processing, thereby greatly improving their melt processing stability.

[0006] To achieve the above objectives, the present invention provides the following technical solution: This invention provides a polyaryletherketone compound having the structure shown in Formula I: Formula I; In formula I, Ar is: ; R is: ; In formula I, n is 1, 2, or 3.

[0007] The present invention also provides a method for preparing the polyaryletherketone material described in the above technical solution, comprising the following steps: The difluorinated monomer, bisphenol monomer, organic solvent, dehydrating agent and salt-forming agent are mixed and a salt-forming reaction is carried out to obtain the polyarylether ketone compound; The difluoro monomer is one or more of 4,4'-difluorobenzophenone, 4,4'-bis(4-fluorobenzoyl)biphenyl, 4,4'-difluorodiphenyl sulfone, 4,4'-bis(4-fluorobenzenesulfonyl)biphenyl, 1,3-bis(4-fluorobenzoyl)benzene and 1,4-bis(4-fluorobenzoyl)benzene; The bisphenol monomer is one or more of hydroquinone, 4,4'-dihydroxydiphenyl ether, biphenyl, bisphenol A, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 1,4-bis(4-hydroxyphenoxy)benzene, bisphenol fluorene, and phenolphthalein.

[0008] Preferably, the molar ratio of the difluorinated monomer to the bisphenol monomer is (2~30):1.

[0009] Preferably, the dehydrating agent is xylene or toluene.

[0010] Preferably, the organic solvent is one or more of diphenyl sulfone, N-methylpyrrolidone, sulfolane, and 1,4-dimethyldiphenyl sulfone; The total mass ratio of the difluorinated monomer and the bisphenol monomer to the organic solvent is 1:(2~10).

[0011] Preferably, the salt-forming agent is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate; the molar ratio of the salt-forming agent to the bisphenol monomer is (1~2):1.

[0012] Preferably, the temperature of the salt formation reaction is 140~220℃.

[0013] This invention also provides the application of the polyaryletherketone compounds described in the above technical solutions or the polyaryletherketone compounds prepared by the above preparation methods as heat stabilizers.

[0014] The present invention also provides the application of the polyaryletherketone compounds described in the above technical solutions or the polyaryletherketone compounds prepared by the above preparation methods in the preparation of polyaryletherketone complexes.

[0015] The present invention also provides a polyaryletherketone complex, which is prepared by a heat stabilizer and a polyaryletherketone polymer; the polyaryletherketone polymer includes one or more of polyetheretherketone, biphenyl polyetheretherketone, polyetherketone, polyetherketone etherketone ketone, and biphenyl-containing semi-crystalline copolymer polyetheretherketone; The heat stabilizer is the polyaryletherketone compound described in the above technical solution.

[0016] This invention provides a polyaryletherketone compound, which is a polyaryletherketone oligomer with a specific structure. Its molecular structure is highly similar to that of the polyaryletherketone resin matrix, thus exhibiting good compatibility. When used as a heat stabilizer, its excellent compatibility allows for uniform distribution within the polyaryletherketone resin matrix. Simultaneously, polyaryletherketone polymers generate free radicals through chain scission at high temperatures. The end-group structure of the heat stabilizer (Formula I) can capture these free radicals, thereby inhibiting cross-linking of the polyaryletherketone polymer and maintaining its stability. The polyaryletherketone compound provided by this invention can significantly inhibit the thermal degradation and cross-linking of polyaryletherketone resins during high-temperature processing, greatly improving its melt processing stability, thermal stability, processability, and product appearance. Furthermore, the process is simple, and it is applicable to various polyaryletherketone resins, possessing significant industrial application value and broad market prospects. Attached Figure Description

[0017] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0018] Figure 1 The 1H-NMR spectra of Examples 1, 4, and Comparative Examples 1-2 are shown below. Figure 2 The following are DSC diagrams for Examples 1, 4, and Comparative Examples 1-2; Figure 3 Crosslinking time data for Comparative Examples 3-5 and Examples 9-10. Detailed Implementation

[0019] This invention provides a polyaryletherketone compound having the structure shown in Formula I: Formula I; In formula I, Ar is: ; R is: ; In formula I, n is 1, 2, or 3.

[0020] This invention provides a method for preparing the polyaryletherketone material described above, comprising the following steps: The difluorinated monomer, bisphenol monomer, organic solvent, dehydrating agent and salt-forming agent are mixed and subjected to a salt-forming reaction to obtain the polyarylether ketone compound.

[0021] In one embodiment of the present invention, the difluoromonomer is one or more of 4,4'-difluorobenzophenone, 4,4'-bis(4-fluorobenzoyl)biphenyl, 4,4'-difluorodiphenyl sulfone, 4,4'-bis(4-fluorobenzenesulfonyl)biphenyl, 1,3-bis(4-fluorobenzoyl)benzene, and 1,4-bis(4-fluorobenzoyl)benzene; the bisphenol monomer is hydroquinone, 4,4'-dihydroxydiphenyl ether, biphenyl hydroquinone, bisphenol A, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, and 1,3-bis(4-fluorobenzoyl)benzene. The salting agent is one or more of 4-bis(4-hydroxyphenoxy)benzene, bisphenol fluorene, and phenolphthalein; the salting agent is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; the organic solvent is one or more of diphenyl sulfone, N-methylpyrrolidone, sulfolane, and 1,4-dimethyldiphenyl sulfone, specifically diphenyl sulfone or sulfolane.

[0022] In one embodiment of the present invention, the molar ratio of the difluorinated monomer to the bisphenol monomer can be (2~30):1, specifically (5~25):1; the molar ratio of the salt-forming agent to the bisphenol monomer can be (1~2):1, specifically (1.2~1.8):1; the mass ratio of the total mass of the difluorinated monomer and the bisphenol monomer to the mass of the organic solvent can be 1:(2~10), specifically 1:(3~8).

[0023] As one embodiment of the present invention, the specific steps of the salt-forming reaction are as follows: A mixture of difluorinated monomer, a portion of organic solvent, a dehydrating agent, and a salt-forming agent is prepared to obtain a difluorinated monomer mixture. After the difluorinated monomer mixture is azeotropically dehydrated under a protective atmosphere, a bisphenol monomer solution is added dropwise to carry out a salt formation reaction.

[0024] In one embodiment of the present invention, the protective atmosphere can be nitrogen; in another embodiment, the azeotropic water-carrying time can be 1-3 hours, specifically 1-2 hours. In yet another embodiment, the azeotropic water-carrying is preferably carried out under stirring conditions.

[0025] In one embodiment of the present invention, the bisphenol monomer solution is obtained by mixing bisphenol monomer and the remaining organic solvent, and the dropping rate of the bisphenol monomer solution is 0.2~0.3 mL / min.

[0026] In one embodiment of the present invention, the temperature of the salt-forming reaction can be 140~220℃, specifically 160~190℃. In another embodiment of the present invention, the time for the salt-forming reaction, based on the time required to completely add the bisphenol monomer solution, can be 4~8 hours, specifically 5~7 hours. The present invention does not particularly limit the heating rate of the reaction; a heating procedure well-known in the art can be followed. In another embodiment of the present invention, the salt-forming reaction is preferably carried out under stirring conditions.

[0027] In one embodiment of the present invention, after the salt formation reaction, the reaction solution is discharged into deionized water to precipitate a solid. The solid is then successively pulverized, washed, and dried to obtain a polyarylether ketone compound. In another embodiment of the present invention, the washing includes sequential water washing and alcohol washing.

[0028] The method described in this invention can synthesize linear trimers with well-defined structures and high purity with high selectivity. Based on this, an iterative synthesis strategy can be employed, using the purified trimer as an intermediate, reacting it with an excess of another functionalized monomer under pseudo-high dilution conditions. Through controlled stepwise coupling, a pentamer with an equally well-defined structure can be further prepared. This iterative extension method can be carried out sequentially according to this principle to synthesize higher polymers (such as heptameric, nonamers, etc.) with specified sequences.

[0029] This invention also provides the application of the polyaryletherketone compounds described in the above technical solutions or the polyaryletherketone compounds prepared by the above preparation methods as heat stabilizers.

[0030] The present invention also provides the application of the polyaryletherketone compounds described in the above technical solutions or the polyaryletherketone compounds prepared by the above preparation methods in the preparation of polyaryletherketone complexes.

[0031] The present invention also provides a polyaryletherketone complex, prepared from a heat stabilizer and a polyaryletherketone polymer; the polyaryletherketone polymer includes one or more of polyetheretherketone, biphenyl polyetheretherketone, polyetherketone, polyetherketone etherketone, and biphenyl-containing semi-crystalline copolymer polyetheretherketone. As one embodiment of the present invention, the mass ratio of the polyaryletherketone polymer to the polyaryletherketone compound can be (99.9~95):(0.1~5), more preferably (99.5~97):(0.5~3).

[0032] This invention also provides a method for preparing the polyaryletherketone complex described in the above technical solution, comprising the following steps: The polyaryletherketone compound is mechanically blended, melt-extruded, granulated, and dried to obtain the polyaryletherketone complex.

[0033] In one embodiment of the present invention, the mixing is carried out in a high-speed mixer. In another embodiment of the present invention, prior to mixing, it is preferable to further dry the polyaryletherketone compound and the polyaryletherketone polymer; the drying temperature can be 80~130℃, specifically 90~120℃; the drying time can be 10~24h, specifically 12~18h.

[0034] In one embodiment of the present invention, the melt blending can be carried out in a twin-screw extruder, wherein the screw speed in the twin-screw extruder is preferably 40 rpm. In another embodiment of the present invention, the melt blending temperature can be 360~395℃, specifically 370~390℃. In yet another embodiment of the present invention, the drying temperature can be 100℃, and the drying time can be 12 hours; the drying can be carried out under vacuum conditions.

[0035] To further illustrate the present invention, the following detailed description of the invention's solutions, in conjunction with the accompanying drawings and embodiments, is provided, but should not be construed as limiting the scope of protection of the present invention.

[0036] Example 1 1250 mL of sulfolane, 12.72 g (0.12 mol) of anhydrous sodium carbonate, 218.2 g (1 mol) of 4,4'-difluorobenzophenone, and 100 mL of xylene were placed in a 3000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to azeotropically remove water for 1 hour, and the water produced in the reaction was removed using a water separator. The reaction system temperature was then raised to 180 °C. 21.42 g (0.1 mol) of 4,4'-dihydroxybenzophenone was dissolved in 250 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 50 mL / 3 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued at 180 °C for 6 hours with stirring to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, washed three times with ethanol, and then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. F3 .

[0037] Example 2 625 mL of sulfolane, 6.36 g (0.06 mol) of anhydrous sodium carbonate, 109.1 g (0.5 mol) of 4,4'-difluorobenzophenone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to azeotropically carry away water for 1 hour, removing the water generated in the reaction using a water separator. The reaction system temperature was then raised to 180 °C. 5.51 g (0.05 mol) of hydroquinone was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued to be stirred at 180 °C for 6 hours to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, and then washed three times with ethanol. It was then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. F3-HQ .

[0038] Example 3 625 mL of sulfolane, 6.36 g (0.06 mol) of anhydrous sodium carbonate, 109.1 g (0.5 mol) of 4,4'-difluorobenzophenone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to azeotropically remove water for 1 hour, and the water produced in the reaction was removed using a water separator. The reaction system temperature was then raised to 180 °C. 12.51 g (0.05 mol) of 4,4'-dihydroxydiphenyl sulfone was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued at 180 °C for 6 hours with stirring to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, washed three times with ethanol, and then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. F3-BPS .

[0039] Example 4 625 mL of sulfolane, 6.36 g (0.06 mol) of anhydrous sodium carbonate, 109.1 g (0.5 mol) of 4,4'-difluorobenzophenone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to azeotropically carry away water for 1 hour, removing the water generated in the reaction using a water separator. The temperature of the reaction system was then raised to 180 °C. 9.31 g (0.05 mol) of biphenyl hydroquinone was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued to be stirred at 180 °C for 6 hours to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, washed three times with ethanol, and then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. F3-BP .

[0040] Example 5 625 mL of sulfolane, 6.36 g (0.06 mol) of anhydrous sodium carbonate, 109.1 g (0.5 mol) of 4,4'-difluorobenzophenone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to azeotropically remove water for 1 hour, and the water generated in the reaction was removed using a water separator. The temperature of the reaction system was then raised to 180 °C. 17.52 g (0.05 mol) of bisphenol fluorene was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued to be stirred at 180 °C for 6 hours to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, washed three times with ethanol, and then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. F3-BPF .

[0041] Example 6 625 mL of sulfolane, 3.18 g (0.03 mol) of anhydrous sodium carbonate, 109.1 g (0.5 mol) of 4,4'-difluorobenzophenone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to undergo an azeotropic dehydration for 1 hour, and the water produced in the reaction was removed using a water separator. The reaction system temperature was then raised to 180 °C. PEK... OH3 12.13 g (0.02 mol) was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. The solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued to be stirred at 180 °C for 6 hours to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, washed three times with ethanol, and then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear pentamer of PEK, denoted as PEK. F5 .

[0042] Example 7 625 mL of sulfolane, 6.36 g (0.06 mol) of anhydrous sodium carbonate, 127.1 g (0.5 mol) of 4,4'-difluorodiphenyl sulfone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to undergo an azeotropic reaction for 1.5 hours, removing the water produced through a water separator. The reaction system temperature was then raised to 190 °C. 5.51 g (0.05 mol) of hydroquinone was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours at 180 °C with constant stirring. After the addition was complete, the reaction mixture was stirred at 190 °C for 7 hours to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, washed three times with ethanol, and then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. F3-DFDPS-HQ .

[0043] Example 8 625 mL of sulfolane, 6.36 g (0.06 mol) of anhydrous sodium carbonate, 127.1 g (0.5 mol) of 4,4'-difluorodiphenyl sulfone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to azeotropically remove water for 1.5 hours, and the water produced in the reaction was removed using a water separator. The temperature of the reaction system was then raised to 190 °C. 12.51 g (0.05 mol) of 4,4'-dihydroxydiphenyl sulfone was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued at 190 °C for 7 hours with stirring to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, washed three times with ethanol, and then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. F3-DFDPS-BPS .

[0044] Comparative Example 1 625 mL of sulfolane, 6.36 g (0.06 mol) of anhydrous sodium carbonate, 100.11 g (0.05 mol) of 4-fluorobenzophenone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to azeotropically remove water for 1 hour, and the water produced in the reaction was removed using a water separator. The reaction system temperature was then raised to 180 °C. 10.71 g (0.05 mol) of 4,4'-dihydroxybenzophenone was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued at 180 °C for 6 hours with stirring to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The resulting solid was pulverized, repeatedly washed with water until neutral, washed three times with ethanol, and then dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. Ph3 .

[0045] Comparative Example 2 625 mL of sulfolane, 63.6 g (0.60 mol) of anhydrous sodium carbonate, 107.11 g (0.5 mol) of 4,4'-dihydroxybenzophenone, and 50 mL of xylene were placed in a 1000 mL four-necked flask equipped with a mechanical stirrer, thermometer, nitrogen inlet, and constant-pressure dropping funnel. Under a nitrogen atmosphere, the reaction mixture was stirred and heated. The temperature was slowly increased to 150 °C and maintained at this temperature to allow the xylene to azeotropically remove water for 1 hour, and the water produced in the reaction was removed using a water separator. The temperature of the reaction system was then raised to 180 °C. 10.91 g (0.05 mol) of 4,4'-difluorobenzophenone was dissolved in 125 mL of sulfolane, and the resulting solution was transferred to a constant-pressure dropping funnel. This solution was slowly added dropwise to the reaction system at a rate of approximately 25 mL / 2 hours under constant stirring at 180 °C. After the addition was complete, the reaction was continued at 180 °C for 6 hours with stirring to ensure complete reaction. The reaction solution was then poured into deionized water under vigorous stirring to precipitate the product. The obtained solid was pulverized, repeatedly washed with acetic acid, washed with water until neutral, and then washed three times with ethanol. Finally, it was dried in a vacuum drying oven at 100 °C for 12 hours to obtain the linear PEK trimer, denoted as PEK. OH3 .

[0046] Example 9 The polyaryletherketone heat stabilizer prepared in Example 1 and polyetherketone (brand name VICTREX HT P45PF, purchased from Victrex) were placed separately in a vacuum drying oven and dried at 100°C for 12 hours. 2.00 parts by weight of the dried heat stabilizer and 98.00 parts by weight of the polyetherketone resin were accurately weighed and thoroughly mixed in a high-speed mixer. The mixture was then added to a twin-screw extruder and dried at 380°C and a screw speed of 40 r / min. -1 The mixture was melt-blended under the specified conditions, extruded and granulated, and the resulting granules were placed in a vacuum drying oven and dried again at 100°C for 12 hours to obtain the high-stability polyetherketone composite 1.

[0047] Example 10 The polyaryletherketone heat stabilizer prepared in Example 4 and polyetherketone (brand name VICTREX HT P45PF, purchased from Victrex) were placed separately in a vacuum drying oven and dried at 100°C for 12 hours. 2.00 parts by weight of the dried heat stabilizer and 98.00 parts by weight of the polyetherketone resin were accurately weighed and thoroughly mixed in a high-speed mixer. The mixture was then added to a twin-screw extruder and dried at 380°C and a screw speed of 40 r / min. -1 The mixture was melt-blended under the specified conditions, extruded and granulated, and the resulting granules were placed in a vacuum drying oven and dried again at 100°C for 12 hours to obtain the high-stability polyetherketone composite 2.

[0048] Example 11 The polyaryletherketone heat stabilizer prepared in Example 2 and polyetherketone (brand name VICTREX HT P45PF, purchased from Victrex) were placed separately in a vacuum drying oven and dried at 100°C for 12 hours. 2.00 parts by weight of the dried heat stabilizer and 98.00 parts by weight of the polyetherketone resin were accurately weighed and thoroughly mixed in a high-speed mixer. The mixture was then added to a twin-screw extruder and dried at 380°C and a screw speed of 40 r / min. -1 The mixture was melt-blended under the specified conditions, extruded and granulated, and the resulting granules were placed in a vacuum drying oven and dried again at 100°C for 12 hours to obtain the highly stable polyetherketone composite 3.

[0049] Example 12 The polyaryletherketone heat stabilizer prepared in Example 8 and polyetherketone (brand name VICTREX HT P45PF, purchased from Victrex) were placed separately in a vacuum drying oven and dried at 100°C for 12 hours. 2.00 parts by weight of the dried heat stabilizer and 98.00 parts by weight of the polyetherketone resin were accurately weighed and thoroughly mixed in a high-speed mixer. The mixture was then added to a twin-screw extruder and dried at 380°C and a screw speed of 40 r / min. -1 The mixture was melt-blended under the specified conditions, extruded and granulated, and the resulting granules were placed in a vacuum drying oven and dried again at 100°C for 12 hours to obtain the high-stability polyetherketone composite 4.

[0050] Comparative Example 3 Polyetherketone (brand name VICTREX HT P45PF, purchased from Victrex) was placed in a vacuum drying oven and dried at 100°C for 12 hours. The dried polyetherketone resin was accurately weighed. The polyetherketone resin was then added to a twin-screw extruder and dried at 380°C and a screw speed of 40 rpm. -1 After melt extrusion and granulation under certain conditions, the resulting granules are placed in a vacuum drying oven and dried again at 100°C for 12 hours to obtain the polyetherketone granules.

[0051] Comparative Example 4 The polyaryletherketone heat stabilizer prepared in Comparative Example 1 and polyetherketone (brand name VICTREX HT P45PF, purchased from Victrex) were placed separately in a vacuum drying oven and dried at 100°C for 12 hours. 2.00 parts by weight of the dried heat stabilizer and 98.00 parts by weight of the polyetherketone resin were accurately weighed and thoroughly mixed in a high-speed mixer. The mixture was then added to a twin-screw extruder and dried at 380°C and a screw speed of 40 r / min.-1 The mixture was melt-blended under the specified conditions, extruded and granulated, and the resulting granules were placed in a vacuum drying oven and dried again at 100°C for 12 hours to obtain the highly stable polyetherketone composite 5.

[0052] Comparative Example 5 The polyaryletherketone heat stabilizer prepared in Comparative Example 2 and polyetherketone (brand name VICTREX HT P45PF, purchased from Victrex) were placed separately in a vacuum drying oven and dried at 100°C for 12 hours. 2.00 parts by weight of the dried heat stabilizer and 98.00 parts by weight of the polyetherketone resin were accurately weighed and thoroughly mixed in a high-speed mixer. The mixture was then added to a twin-screw extruder and dried at 380°C and a screw speed of 40 r / min. -1 The mixture was melt-blended under the specified conditions, extruded and granulated, and the resulting granules were placed in a vacuum drying oven and dried again at 100°C for 12 hours to obtain the highly stable polyetherketone composite 6.

[0053] Figure 1 The products obtained in Examples 1, 4, 1, and 2 are... 1 H-NMR spectrum, Figure 1 This confirms the successful synthesis of polyaryletherketone compounds.

[0054] Figure 2 The DSC charts for Examples 1, 4, Comparative Example 1, and Comparative Example 2 are shown below. Figure 2 It can be seen that the melting point of Example 1 is 280.30℃, the melting point of Example 4 is 283.97℃, the melting point of Comparative Example 1 is 244.28℃, and the melting point of Comparative Example 2 is 248.43℃.

[0055] Figure 3 The crosslinking time data for Comparative Examples 3-5 and Examples 9-10 of this invention are shown in the diagram. The crosslinking time data are based on the test results of a flat plate rheometer. According to ASTM D4473, the junction of elastic modulus (G') and viscous modulus (G''), i.e., G'' / G'=1, is defined as the gel point of the thermosetting resin (this patent borrows this standard). The effect is judged by measuring the junction of elastic modulus (G') and viscous modulus (G'') through rheological testing. Compared with Comparative Example 3, Example 9 shows an improvement of 27.60%, Example 10 shows an improvement of 39.27%, Comparative Example 4 shows an improvement of 10.66%, and Comparative Example 5 shows a decrease of 31.68%.

[0056] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, not all embodiments. Other embodiments can be obtained based on these embodiments without creative intent, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A polyaryletherketone compound, characterized in that, It has the structure shown in Equation I: Formula I; In formula I, Ar is: ； R is: ； In Equation I, n is 1, 2, or 3.

2. The method for preparing the polyaryletherketone material according to claim 1, comprising the following steps: The difluorinated monomer, bisphenol monomer, organic solvent, dehydrating agent and salt-forming agent are mixed and a salt-forming reaction is carried out to obtain the polyarylether ketone compound; The difluoro monomer is one or more of 4,4'-difluorobenzophenone, 4,4'-bis(4-fluorobenzoyl)biphenyl, 4,4'-difluorodiphenyl sulfone, 4,4'-bis(4-fluorobenzenesulfonyl)biphenyl, 1,3-bis(4-fluorobenzoyl)benzene and 1,4-bis(4-fluorobenzoyl)benzene; The bisphenol monomer is one or more of hydroquinone, 4,4'-dihydroxydiphenyl ether, biphenyl, bisphenol A, 4,4'-dihydroxybenzophenone, 4,4'-dihydroxydiphenyl sulfone, 1,4-bis(4-hydroxyphenoxy)benzene, bisphenol fluorene, and phenolphthalein.

3. The preparation method according to claim 2, characterized in that, The molar ratio of the difluorinated monomer to the bisphenol monomer is (2~30):

1.

4. The preparation method according to claim 2, characterized in that, The water-removing agent is xylene or toluene.

5. The preparation method according to claim 2, characterized in that, The organic solvent is one or more of diphenyl sulfone, N-methylpyrrolidone, sulfolane, and 1,4-dimethyldiphenyl sulfone; The total mass ratio of the difluorinated monomer and the bisphenol monomer to the organic solvent is 1:(2~10).

6. The preparation method according to claim 2, characterized in that, The salt-forming agent is one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; the molar ratio of the salt-forming agent to the bisphenol monomer is (1~2):

1.

7. The preparation method according to claim 2, characterized in that, The temperature for the salt formation reaction is 140~220℃.

8. The use of the polyaryletherketone compound of claim 1 or the polyaryletherketone compound prepared by any one of claims 2 to 7 as a heat stabilizer.

9. The use of the polyaryletherketone compound of claim 1 or the polyaryletherketone compound prepared by the preparation method of any one of claims 2 to 7 in the preparation of polyaryletherketone complexes.

10. A polyaryletherketone complex, characterized in that, It is prepared by heat stabilizer and polyaryletherketone polymer; the polyaryletherketone polymer includes one or more of polyetheretherketone, biphenyl polyetheretherketone, polyetherketone, polyetherketone etherketone ketone, and biphenyl-containing semi-crystalline copolymer polyetheretherketone; The heat stabilizer is the polyaryletherketone compound as described in claim 1.

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