Preparation method of polyaryletherketone

Abstract

The invention relates to the technical field of high-performance polymer synthesis, in particular to a preparation method of polyaryletherketone, which comprises the following steps: S1, under the condition of inert gas, adding dihalogenated benzophenone and bisphenol fluorene into a solvent, uniformly mixing, adding alkali carbonate, and reacting under the condition of heating to obtain an oligomer; s2, adding aromatic diphenol into the system in the step S1 in batches, and carrying out temperature programming reaction to obtain a block copolymer; and S3, adding an end-capping reagent into the system to carry out end-capping reaction, and after the reaction is finished, carrying out post-treatment to obtain the polyaryletherketone. According to the preparation method of the polyaryletherketone, a feeding mode of gradient segmented feeding is adopted, a polymerization process of low-temperature pre-polycondensation and high-temperature chain extension copolymerization is developed, the reaction rate is controllable, sequence distribution is uniform, and product performance is stable. In addition, the preparation method can effectively reduce energy consumption and is more beneficial to industrial production.

Description

Technical Field

[0001] The present invention relates to a method for preparing polyaryletherketone, belonging to the technical field of high-performance polymer synthesis. Background Art

[0002] Polyaryletherketone belongs to semi-crystalline thermoplastic materials and has excellent properties such as high temperature resistance, high strength, high modulus, high insulation, corrosion resistance, good dimensional stability and easy processing. It is an engineering plastic with excellent comprehensive properties and is widely used in the fields of electronics, machinery, automobiles, airplanes, food and medicine, and aerospace.

[0003] The traditional preparation methods of polyaryletherketone are mainly divided into nucleophilic substitution method and electrophilic substitution method. With the development of industrialization, the nucleophilic substitution method gradually occupies the dominant position due to its advantages such as excellent purity and crystallinity of the prepared products, and has become the core method for industrial production of polyaryletherketone. The patent applications with publication numbers US4176222A, US4320224A and US4331798A all describe the preparation of polyaryletherketone by the nucleophilic substitution method, that is, various aromatic polyethers containing -SO2- or -CO- groups (collectively referred to as polyaryletherketone materials) are prepared using different bisphenols and aromatic dihalides, and then the effects on the properties of polyaryletherketone materials are explored by changing factors such as alkali metal salts and solvents. With the in-depth research and development of polyaryletherketone, polyetheretherketone (PEEK) stands out from many polyaryletherketone materials due to its excellent properties and has become one of the high-performance polymers that countries are competing to develop. Taking the nucleophilic substitution preparation method of PEEK as an example, its reaction process is as follows: ; Wherein, X represents a halogen (F, Cl, Br, etc.); R1 represents C 6-30 Aromatic hydrocarbon groups and their halogenated derivatives, etc.; R2 represents a monovalent C 1-13 Organic groups, phenyl, biphenyl, etc.

[0004] The above traditional methods usually involve reacting two or more reactants in an equimolar ratio according to functional groups or with a slight excess of aromatic dihalides. The reactions have problems such as harsh synthesis conditions, high energy consumption, high costs, and certain pollution from by-products. First, in terms of synthesis, traditional polyetheretherketone has strict requirements for the purity of raw materials, inert atmosphere, temperature control, and reaction time during preparation, which makes the preparation conditions of the product extremely harsh. Second, most of the currently disclosed reaction temperatures are not lower than 310 °C, with a relatively high reaction temperature and a long reaction time, greatly increasing energy consumption and being very unfavorable for industrial production. Finally, considering the recycling aspect, due to raw material costs, it is necessary to recycle solvents and by-products after the reaction. Therefore, a large amount of organic reagents are used in the post-treatment, ultimately generating a large amount of waste solvents and alkaline wastewater, with high costs for treating the three wastes and environmental pollution.

[0005] Currently, in addition to optimizing the types of raw materials and preparation processes used in traditional preparation methods, the mainstream development direction of polyaryletherketone is also to improve the performance of polyaryletherketone by introducing new comonomers. For example, the patent with the publication number CN100582133C discloses a preparation method of polyetheretherketone. A new type of polyaryletherketone product is prepared by copolymerizing biphenol, hydroquinone, and 4,4'-difluorobenzophenone. Although this product has a higher melting point and melt viscosity compared to traditional PEEK materials, its mechanical strength is relatively poor. The patent with the publication number CN101245139B discloses a preparation method of a polyetherketone and polyetheretherketone terpolymer. 4,4'-dihydroxybenzophenone, hydroquinone, and 4,4'-difluorobenzophenone are used for copolymerization to prepare a fluorine-terminated polyaryletherketone. This material has high thermal stability, but the preparation temperature is relatively high (it needs to be raised to 320 °C and react for 3 - 5 h), with high energy consumption and being unfavorable for large-scale production. The patent application with the publication number CN116515101A discloses a semi-crystalline biphenyl copolymerized polyetheretherketone resin and its preparation method. In the preparation method, sulfolane is used as a solvent and xylene is used as a water-carrying agent. Bisphenol fluorene, biphenol, and 4,4'-difluorobenzophenone are used to prepare a high-temperature-resistant polyaryletherketone. The polymerization temperature of this preparation method is relatively low and the post-treatment process is relatively simple. However, the reaction is more demanding. During the dehydration stage, due to the relatively high co-boiling point of xylene and sulfolane, it is difficult to completely remove xylene, resulting in a relatively low conversion rate of the final reaction. Secondly, when introducing the bisphenol fluorene monomer, due to its large steric hindrance effect, it is often difficult to evenly graft it onto the main chain, which also affects the performance of the final product.

[0006] Therefore, it is of great value to develop a preparation method for polyaryletherketone materials that can achieve low energy consumption, high efficiency in production, a wider range of application fields, and easy processing. Summary of the Invention

[0007] In view of the deficiencies in the prior art, the present invention provides a method for preparing polyaryletherketone. The process conditions in the preparation method are mild, with low energy consumption, suitable for industrial application, and the obtained polyaryletherketone has higher mechanical strength, chemical corrosion resistance and processability.

[0008] The technical solution of the present invention to solve the above technical problems is as follows: A method for preparing polyaryletherketone, the preparation method is: S1. Under an inert gas condition, add dihalodibenzophenone and bisphenol fluorene into a solvent and mix evenly, then add an alkali metal carbonate, and react under heating conditions to obtain an oligomer; S2. Add aromatic dihydric phenol to the system in step S1 in batches, and carry out a programmed temperature rise reaction to obtain a block copolymer; S3. Add a capping agent to the system for capping reaction, and after the reaction is completed, obtain polyaryletherketone through post-treatment.

[0009] Further, the dihalodibenzophenone is at least one of 2,4'-difluorobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone; The aromatic dihydric phenol is at least one of hydroquinone, resorcinol, biphenyl diol, bisphenol A, phenolphthalein.

[0010] Further, the molar ratio of the total molar amount of bisphenol fluorene and aromatic dihydric phenol to the dihalodibenzophenone is 1:(0.95 - 1.15); the molar ratio of the aromatic dihydric phenol to the bisphenol fluorene is 1:(0.1 - 0.8).

[0011] Further, the molar ratio of the total molar amount of bisphenol fluorene and aromatic dihydric phenol to the alkali metal carbonate is 1:(0.98 - 1.30); The alkali metal carbonate is at least one of potassium carbonate, sodium carbonate and cesium carbonate.

[0012] Further, the alkali metal carbonate is a combination of sodium carbonate and potassium carbonate, and the molar ratio of sodium carbonate to potassium carbonate is 1:(0.01 - 0.5).

[0013] Further, the solvent is any one of sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, diphenyl sulfone, dimethyl sulfoxide, N-methylpyrrolidone.

[0014] Further, the capping agent is at least one of 4-fluorobenzophenone, 4-chlorobenzophenone, 4-fluorobiphenyl; The dosage of the capping agent and the total molar amount of bisphenol fluorene and aromatic dihydric phenol are in a ratio of (0.01 - 0.05):1.

[0015] Further, in step S1, the reaction temperature is 150 - 180 °C, and the reaction time is 0.5 - 2 h.

[0016] Further, in step S2, the aromatic diol is added to the reaction system in three batches. After the first batch of aromatic diol is added to the system, the temperature is raised to 180 - 230 °C, and the reaction is carried out for 0.5 - 2 h; after the second batch of aromatic diol is added to the system, the temperature is raised to 230 - 270 °C, and the reaction is carried out for 0.5 - 2 h; after the third batch of aromatic diol is added to the system, the temperature is raised to 270 - 300 °C, and the reaction is carried out for 0.5 - 2 h.

[0017] Further, in step S3, the post-treatment operation method is as follows: after the reaction is completed, the product is poured into cold water for cooling and solidification. After taking the solid and crushing it, it is washed and dried to obtain the polyaryletherketone product.

[0018] The beneficial effects of the present invention are as follows: (1) Compared with the traditional process, the preparation method of the polyaryletherketone of the present invention adopts a feeding method of gradient segmented feeding and develops a polymerization process of low-temperature pre-polycondensation and high-temperature chain extension copolymerization, avoiding the problems of difficult control of the reaction rate, wide molecular weight distribution caused by the "one-pot" feeding method, and large difference in the reaction activities of bisphenol fluorene and hydroquinone, resulting in uneven sequence distribution and poor performance stability of the final product. In addition, the polymerization reaction temperature (270 - 300 °C) of the preparation method of the present invention is more than 10% lower than that of the traditional PAEK preparation process (300 - 340 °C), which can effectively reduce energy consumption. Therefore, the preparation method of the present invention is more conducive to industrial production.

[0019] (2) Compared with the traditional method, the preparation method of the polyaryletherketone of the present invention introduces bisphenol fluorene as a block copolymerization monomer. The fluorene ring of bisphenol fluorene can restrict the free rotation of the polymer chain segment, reduce the thermal motion of the molecular chain at high temperature, and enhance the molecular chain rigidity, thereby improving the thermal stability of the material. Secondly, the steric hindrance of the fluorene ring increases the molecular chain spacing and reduces the chain slip between chains, which can improve the tensile strength and creep resistance of the product. In addition, the fused benzene ring hydrophobic group of the fluorene ring can reduce the penetration of polar solvent molecules (such as concentrated sulfuric acid, DMF) into the polymer matrix, thereby improving the chemical corrosion resistance of the product. Finally, by precisely controlling the content of bisphenol fluorene in the molecular chain (10% - 70%), the rigidity and toughness of the material can be balanced, and a material can be truly fully adapted to a variety of different fields.

[0020] (3) Compared with traditional polyaryletherketone (taking PEEK as an example), the polyaryletherketone product prepared by the preparation method of the present invention has higher mechanical strength (tensile strength ≥ 120 MPa, tensile modulus ≥ 4.5 GPa) and chemical corrosion resistance (strength retention rate in strong acid / strong base environment increased from 82% to 95%) while maintaining excellent high temperature resistance (thermal decomposition temperature ≥ 550 °C) and wear resistance. In downstream applications, efficient injection molding of the material can be achieved by adjusting the processing temperature (350 - 380 °C) and screw speed (60 - 80 rpm), or products with different properties can be produced by controlling the proportion of bisphenol fluorene introduced in the preparation method to flexibly adapt to different application scenarios (such as low melt viscosity is required for electronic packaging parts, and high acid resistance stability is required for chemical corrosion prevention, etc.). Description of the Drawings

[0021] Figure 1 For the comparison of the tensile curves of the polyaryletherketone products of Example 1 and Comparative Example 1; Figure 2 For the TGA curve of the polyaryletherketone prepared in Example 1. Detailed Description of the Invention

[0022] The following is a detailed description of the specific embodiments of the present invention. The present invention can be implemented in many other ways different from those described herein. Those skilled in the art can make similar improvements without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used are only for describing specific embodiments and do not limit the present invention.

[0024] A preparation method of polyaryletherketone, the preparation method is as follows: S1. Under inert gas conditions, add dihalodibenzophenone and bisphenol fluorene into a solvent, heat up to all monomers are completely melted, and then add alkali metal carbonate, and carry out stirring reaction under heating conditions to obtain an oligomer; S2. Add aromatic dihydric phenol to the system of step S1 in batches, and carry out programmed temperature rise stirring reaction to obtain a block copolymer; S3. Add a capping agent to the system for capping reaction, and after the reaction is completed, obtain polyaryletherketone through post-treatment.

[0025] Specifically, the dihalodibenzophenone is at least one of 2,4'-difluorobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-dibromobenzophenone; The aromatic dihydroxybenzene is at least one of hydroquinone, resorcinol, biphenyl diol, bisphenol A, and phenolphthalein.

[0026] Preferably, the dihalobenzophenone is 4,4'-difluorobenzophenone, and the aromatic dihydroxybenzene is hydroquinone.

[0027] Specifically, the molar ratio of the total molar amount of bisphenol fluorene and aromatic dihydroxybenzene to the dihalobenzophenone is 1:(0.95 - 1.15); the molar ratio of the aromatic dihydroxybenzene to bisphenol fluorene is 1:(0.1 - 0.8).

[0028] Preferably, the molar ratio of the total molar amount of bisphenol fluorene and aromatic dihydroxybenzene to the dihalobenzophenone is 1:(0.99 - 1.05); the molar ratio of the aromatic dihydroxybenzene to bisphenol fluorene is 1:(0.1 - 0.7).

[0029] Specifically, the molar ratio of the total molar amount of bisphenol fluorene and aromatic dihydroxybenzene to the alkali metal carbonate is 1:(0.98 - 1.30); The alkali metal carbonate is at least one of potassium carbonate, sodium carbonate, and cesium carbonate.

[0030] Preferably, the molar ratio of the total molar amount of bisphenol fluorene and aromatic dihydroxybenzene to the alkali metal carbonate is 1:(0.99 - 1.20).

[0031] Preferably, the alkali metal carbonate is a combination of sodium carbonate and potassium carbonate, and the molar ratio of sodium carbonate to potassium carbonate is 1:(0.01 - 0.5).

[0032] Specifically, the solvent is any one of sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, diphenyl sulfone, dimethyl sulfoxide, and N-methylpyrrolidone.

[0033] Preferably, the solvent is sulfolane.

[0034] Specifically, the capping agent is at least one of 4-fluorobenzophenone, 4-chlorobenzophenone, and 4-fluorobiphenyl; The dosage of the capping agent and the total molar amount of bisphenol fluorene and aromatic dihydroxybenzene are in a ratio of (0.01 - 0.05):1.

[0035] Preferably, the capping agent is 4-fluorobenzophenone.

[0036] Specifically, in step S1, the reaction temperature is 150 - 180 °C, and the reaction time is 0.5 - 2 h.

[0037] Specifically, in step S2, the aromatic diol is added to the reaction system in three batches. After the first batch of aromatic diol is added to the system, the temperature is raised to 180-230 °C and the reaction is carried out for 0.5-2 h; after the second batch of aromatic diol is added to the system, the temperature is raised to 230-270 °C and the reaction is carried out for 0.5-2 h; after the third batch of aromatic diol is added to the system, the temperature is raised to 270-300 °C and the reaction is carried out for 0.5-2 h.

[0038] Specifically, in step S3, the reaction temperature for adding the capping agent for reaction is 140-330 °C, and the reaction time is 0.5-3 h.

[0039] Preferably, in step S3, the reaction temperature for adding the capping agent for reaction is 250-330 °C, and the reaction time is 0.5-1 h.

[0040] Specifically, in step S3, the post-treatment operation method is as follows: after the reaction is completed, the product is poured into cold water to cool and solidify. After taking the solid and crushing it, it is washed and dried to obtain the polyaryletherketone product.

[0041] More specifically, the post-treatment operation process includes: crushing, washing, filtering, and drying to obtain a powdery finished polyaryletherketone, and then through melt extrusion, air cooling, and pelletizing to obtain a granular finished polyaryletherketone.

[0042] The filtration methods include but are not limited to pressure filtration, vacuum filtration, and centrifugal filtration, and pressure filtration is preferred; the solvents for washing include but are not limited to methanol, toluene, xylene, ethanol, ether, isopropanol, acetone, and water, etc., and acetone and water are preferred; during washing, 2-3 times the amount (based on the weight of the washed crude product) of acetone and water are used respectively for multiple reflux washings until all solvents and by-products are removed, and then the purified product is dried in an oven.

[0043] The drying method is atmospheric drying or negative pressure drying, and atmospheric drying is preferred; the drying time is 0.5-12 hours, and 3-5 hours is preferred; the drying temperature is 80-200 °C, and 150-200 °C is preferred.

[0044] Specifically, the selection of the inert gas includes but is not limited to one or more of nitrogen, helium, neon, argon, etc., and nitrogen is preferred.

[0045] Specifically, the structure of the polyaryletherketone is as shown below, but is not limited to the following: ; Among them, n and m are respectively integers from 1 to 200.

[0046] n is preferably an integer from 80 to 200, and m is preferably an integer from 1 to 80.

[0047] In the following examples, the performance evaluation methods and standards for polyaryletherketone products are as follows: (1) The weight-average molecular weight (Mw) and polydispersity index (PDI) of the polyaryletherketone are obtained by testing after dissolving in dichloroacetic acid at 120 °C through gel permeation chromatography (GPC). The Mw range is ≥10,000 Daltons, preferably ≥20,000 Daltons, more preferably ≥30,000 Daltons; the PDI range is ≤2.00, preferably ≤1.50, more preferably ≤1.20.

[0048] (2) The thermal decomposition temperature (Td(1%)) of the polyaryletherketone is tested using a thermogravimetric analyzer (TGA) according to the standard ASTM E1131. The Tg range is ≥500.0 °C, preferably ≥530.0 °C, more preferably ≥550.0 °C.

[0049] (3) The tensile strength, tensile modulus, and elongation at break of the polyaryletherketone are tested using a universal material testing machine according to the standard ASTM D638. The tensile strength range is ≥70.0 MPa, preferably ≥90.0 MPa, more preferably ≥100.0 MPa; the tensile modulus range is ≥3000.0 MPa, preferably ≥3500.0 MPa, more preferably ≥4000.0 MPa; the elongation at break is ≥1.0%, preferably ≥10.0%, more preferably ≥20.0%.

[0050] (4) The melt flow index of the polyaryletherketone is tested using a melt indexer according to the standard ASTM D1238 under the conditions of a 5-kilogram (kg) weight and a temperature of 380 °C. The melt flow index range is 3.0 - 30.0 g / 10 min, preferably 5.0 - 25.0 g / 10 min, more preferably 8.0 - 15.0 g / 10 min.

[0051] (5) The acid resistance strength retention rate of the polyaryletherketone is tested by soaking test specimens in 98% concentrated sulfuric acid at room temperature (23 ± 2 °C, 50 ± 10% humidity) for 48 h and then performing tensile strength performance testing according to the standard ASTM D543. The acid resistance strength retention rate range is 50% - 99%, preferably 80% - 99%, more preferably 90% - 99%.

[0052] The information on the key raw materials involved in the examples is as follows (the rest of the raw materials are ordinary commercially available industrial products): (1) 4,4'-Difluorobenzophenone, with a purity of ≥99.0%, purchased from Kangda New Materials Co., Ltd.

[0053] (2) Hydroquinone, with a purity of ≥99.5%, purchased from Jinan Century Tongda Chemical Co., Ltd.

[0054] (3) Bisphenol fluorene, purity ≥ 98.0%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0055] (4) Diphenyl sulfone, purity ≥ 99.5%, purchased from Shandong Dibek Biotechnology Co., Ltd.

[0056] (5) 4-Fluorobenzophenone, purity ≥ 99.0%, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

[0057] (6) Sodium carbonate, purity ≥ 99.0%, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0058] (7) Potassium carbonate, purity ≥ 99.0%, purchased from Sinopharm Chemical Reagent Co., Ltd.

[0059] Example 1 A preparation method of polyaryletherketone, the preparation method is as follows: S1. A 2L three-necked flask equipped with a mechanical stirrer, a thermometer, and a water separator was evacuated, and then filled with high-purity nitrogen (≥99.99%). The air atmosphere in the system was replaced with a nitrogen atmosphere by evacuating and filling with nitrogen more than three times, and a certain flow rate of nitrogen was continuously introduced to maintain. 500 g of diphenyl sulfone (2.29 mol), 4,4'-difluorobenzophenone (1.00 mol), and bisphenol fluorene (0.10 mol) were added to the three-necked flask. After heating to 160 °C until all of them melted, sodium carbonate (0.70 mol) and potassium carbonate (0.35 mol) were added, and the reaction was carried out at 160 °C for 1 h to obtain an oligomer.

[0060] S2. Hydroquinone (0.90 mol) as the reactant was divided into three equal parts and added to the reaction system in three batches. After the first batch of hydroquinone (0.30 mol) was added to the system, the temperature was raised to 200 °C and the reaction was carried out for 1 h; after the second batch of hydroquinone (0.30 mol) was added to the system, the temperature was raised to 230 °C and the reaction was carried out for 1 h; after the third batch of hydroquinone (0.30 mol) was added to the system, the temperature was raised to 280 °C and the reaction was carried out for 2 h to obtain a block copolymer.

[0061] S3. At 280 °C, 4-fluorobenzophenone (0.02 mol) was added for capping for 0.5 h and then poured out. The crude product was crushed and washed by refluxing with acetone and deionized water for several times until impurities such as diphenyl sulfone and inorganic salts in the product were completely removed to obtain a powdery product, and then it was extruded, granulated, and injection-molded, and its performance was evaluated.

[0062] In this example, the total molar ratio of bisphenol fluorene and aromatic diol to the molar ratio of the dihalodiphenyl ketone is 1:1; the molar ratio of aromatic diol to bisphenol fluorene is 1:0.11; The molar ratio of the total number of moles of bisphenol fluorene and aromatic diol to the molar amount of the alkali metal carbonate is 1:1.05; The molar ratio of sodium carbonate to potassium carbonate is 1:0.5; The dosage of the end-capping agent and the total molar number of bisphenol fluorene and aromatic diol is in a ratio of 0.02:1.

[0063] Example 2 Under the same reaction conditions and preparation method as in Example 1, the difference is that in this Example 2, the input amount of bisphenol fluorene is increased to 0.25 mol, and the single charge amount of hydroquinone is reduced to 0.25 mol.

[0064] Example 3 Under the same reaction conditions and preparation method as in Example 1, the difference is that in this Example 3, the input amount of bisphenol fluorene is increased to 0.40 mol, and the single charge amount of hydroquinone is reduced to 0.20 mol.

[0065] Example 4 Under the same reaction conditions and preparation method as in Example 1, the difference is that in this Example 4, all of the input alkali metal salts are replaced with sodium carbonate, that is, 1.10 mol of sodium carbonate is added.

[0066] Example 5 Under the same reaction conditions and preparation method as in Example 1, the difference is that in this Example 5, the input alkali metal salts are replaced with 0.55 mol of sodium carbonate and 76.02 g of potassium carbonate, and the experimental results are shown in Table 1.

[0067] Example 6 A method for preparing polyaryletherketone, the preparation method is as follows: S1. A 2 L three-necked flask equipped with a mechanical stirrer, a thermometer, and a water separator is evacuated to vacuum, and then filled with high-purity nitrogen (≥99.99%). The air atmosphere in the system is fully replaced with a nitrogen atmosphere by evacuating to vacuum more than three times, and a certain flow rate of nitrogen is continuously introduced for maintenance. 500 g of N,N-dimethylformamide, 2,4'-difluorobenzophenone (1.15 mol), and bisphenol fluorene (0.30 mol) are added to the three-necked flask. After heating to 150 °C until all of them are melted, sodium carbonate (1 mol) and potassium carbonate (0.3 mol) are added, and the reaction is carried out at 150 °C for 2 h to obtain an oligomer.

[0068] S2. Divide the reactant resorcinol (0.70 mol) into three portions and add them to the reaction system in three batches. After adding the first portion of resorcinol (0.20 mol) to the system, raise the temperature to 180 °C and react for 2 h; after adding the second portion of resorcinol (0.30 mol) to the system, raise the temperature to 260 °C and react for 0.5 h; after adding the third portion of resorcinol (0.20 mol) to the system, raise the temperature to 300 °C and react for 1 h to obtain a block copolymer.

[0069] S3. At 300 °C, add 4-chlorobenzophenone (0.01 mol) for end-capping for 0.5 h and then pour out. Crush the crude product and perform multiple reflux washings with acetone and deionized water respectively until the solvents and inorganic salts and other impurities in the product are completely removed to obtain a powdery product, and then perform extrusion, granulation and injection molding and evaluate its performance.

[0070] In this example, the molar ratio of the total molar amount of bisphenol fluorene and aromatic diol to the molar amount of the dihalodiphenyl ketone is 1:1.15; the molar ratio of aromatic diol to bisphenol fluorene is 1:0.43; The molar ratio of the total molar amount of bisphenol fluorene and aromatic diol to the alkali metal carbonate is 1:1.30; The molar ratio of sodium carbonate to potassium carbonate is 1:0.3; The dosage ratio of the end-capping agent to the total molar amount of bisphenol fluorene and aromatic diol is 0.01:1.

[0071] Example 7 A preparation method of polyaryletherketone, and the preparation method is as follows: S1. Evacuate a 2 L three-necked flask equipped with a mechanical stirrer, a thermometer and a water separator to vacuum, and then fill it with high-purity nitrogen (≥99.99%). Evacuate the system more than three times to fully replace the air atmosphere in the system with a nitrogen atmosphere, and continuously introduce a certain flow rate of nitrogen for maintenance. Add 500 g of dimethyl sulfoxide, 4,4'-dichlorobenzophenone (0.95 mol) and bisphenol fluorene (0.35 mol) to the three-necked flask. After raising the temperature to 180 °C and waiting for it to completely melt, add sodium carbonate (0.9 mol) and potassium carbonate (0.08 mol), and react at 180 °C for 0.5 h to obtain an oligomer.

[0072] S2. Divide the reactant bisphenol A (0.65 mol) into three portions and add them to the reaction system in three batches. After adding the first portion of bisphenol A (0.20 mol) to the system, raise the temperature to 230 °C and react for 0.5 h; after adding the second portion of bisphenol A (0.25 mol) to the system, raise the temperature to 270 °C and react for 1 h; after adding the third portion of bisphenol A (0.20 mol) to the system, raise the temperature to 290 °C and react for 1.5 h to obtain a block copolymer.

[0073] S3. At 300 °C, add 4-fluorobiphenyl (0.05 mol) for end-capping for 1 h and then pour out. Crush the crude product and perform multiple reflux washings with acetone and deionized water respectively until the solvents, inorganic salts and other impurities in the product are completely removed to obtain a powdery product, and then perform extrusion, granulation and injection molding and evaluate its performance.

[0074] In this example, the total molar ratio of bisphenol fluorene and aromatic diol to the molar ratio of the dihalodiphenyl ketone is 1:0.95; the molar ratio of aromatic diol to bisphenol fluorene is 1:0.54; The total molar ratio of bisphenol fluorene and aromatic diol to the molar ratio of the alkali metal carbonate is 1:1.30; The molar ratio of sodium carbonate to potassium carbonate is 1:0.09; The dosage ratio of the end-capping agent to the total molar amount of bisphenol fluorene and aromatic diol is 0.05:1.

[0075] Comparative Example 1 Under the same reaction conditions and preparation method as in Example 1, the difference is that in this Comparative Example 1, all bisphenol fluorene is replaced with hydroquinone, and the specific steps are as follows: S1. Evacuate a 2 L three-necked flask equipped with a mechanical stirrer, a thermometer and a water separator to vacuum, and then fill it with high-purity nitrogen (≥99.99%). Evacuate the system more than three times to fully replace the air atmosphere in the system with a nitrogen atmosphere, and continuously introduce a certain flow rate of nitrogen to maintain it. Add 500 g of diphenyl sulfone (2.29 mol), 4,4'-difluorobenzophenone (1.00 mol) and hydroquinone (0.10 mol) into the three-necked flask. After heating to 160 °C and waiting for it to completely melt, add sodium carbonate (0.70 mol) and potassium carbonate (0.35 mol), and react at 160 °C for 1 h to obtain an oligomer.

[0076] S2. Divide the reactant hydroquinone (0.90 mol) into three equal parts and add them to the reaction system in three batches. After the first batch of hydroquinone (0.30 mol) is added to the system, heat it to 200 °C and react for 1 h; after the second batch of hydroquinone (0.30 mol) is added to the system, heat it to 230 °C and react for 1 h; after the third batch of hydroquinone (0.30 mol) is added to the system, heat it to 280 °C and react for 2 h to obtain a block copolymer.

[0077] S3. At 280 °C, add 4-fluorobenzophenone (0.02 mol) to cap for 0.5 h and then pour out. Crush the crude product and conduct multiple reflux washings with acetone and deionized water respectively until impurities such as diphenyl sulfone and inorganic salts in the product are completely removed to obtain a powdery product. Then, perform extrusion, granulation, and injection molding and evaluate its performance.

[0078] In this example, the molar ratio of the total molar amount of aromatic diol to the molar amount of the dihalodiphenyl ketone is 1:1; the molar ratio of the total molar amount of aromatic diol to the molar amount of the alkali metal carbonate is 1:1.05; the molar ratio of sodium carbonate to potassium carbonate is 1:0.5; the dosage ratio of the capping agent to the total molar amount of aromatic diol is 0.02:1.

[0079] Comparative Example 2 Under the same reaction conditions and preparation method as in Example 1, the difference is that in this Comparative Example 2, all the hydroquinone added in the feedstock is replaced with bisphenol fluorene and merged with the first feedstock, and 1.00 mol of bisphenol fluorene is added in one-time feedstock. The specific steps are as follows: S1. Evacuate a 2 L three-necked flask equipped with a mechanical stirrer, thermometer, and water separator to vacuum, and then fill it with high-purity nitrogen (≥99.99%). Evacuate the system to vacuum more than three times to fully replace the air atmosphere in the system with a nitrogen atmosphere, and continuously introduce nitrogen with a certain flow rate to maintain it. Add 500 g of diphenyl sulfone (2.29 mol), 4,4'-difluorobenzophenone (1.00 mol), and bisphenol fluorene (1.00 mol) to the three-necked flask. After heating to 160 °C until all of them melt, add sodium carbonate (0.70 mol) and potassium carbonate (0.35 mol), and react at 160 °C for 5 h.

[0080] S2. At 280 °C, add 4-fluorobenzophenone (0.02 mol) to cap for 0.5 h and then pour out. Crush the crude product and conduct multiple reflux washings with acetone and deionized water respectively until impurities such as diphenyl sulfone and inorganic salts in the product are completely removed to obtain a powdery product. Then, perform extrusion, granulation, and injection molding and evaluate its performance.

[0081] In this example, the molar ratio of the total molar amount of bisphenol fluorene to the molar amount of the dihalodiphenyl ketone is 1:1; the molar ratio of bisphenol fluorene is 1:0.11; the molar ratio of the total molar amount of bisphenol fluorene to the molar amount of the alkali metal carbonate is 1:1.05; the molar ratio of sodium carbonate to potassium carbonate is 1:0.5; the dosage ratio of the capping agent to the total molar amount of bisphenol fluorene is 0.02:1.

[0082] Comparative Example 3 The same reaction conditions and preparation method as in Example 1, the difference is that: in step S2 of this Comparative Example 3, hydroquinone is fed in one go, and the specific steps are as follows: S1. A 2L three-necked flask equipped with a mechanical stirrer, a thermometer, and a water separator was evacuated and then filled with high-purity nitrogen (≥99.99%). It was evacuated more than three times to fully replace the air atmosphere in the system with a nitrogen atmosphere, and a certain flow rate of nitrogen was continuously introduced to maintain it. 500 g of diphenyl sulfone (2.29 mol), 4,4'-difluorobenzophenone (1.00 mol), and bisphenol fluorene (0.10 mol) were added to the three-necked flask. After heating to 160 °C until all of them melted, sodium carbonate (0.70 mol) and potassium carbonate (0.35 mol) were added, and the reaction was carried out at 160 °C for 1 h to obtain an oligomer.

[0083] S2. The reactant hydroquinone (0.90 mol) was added to the reaction system, heated to 200 °C, and reacted for 1 h; then heated to 230 °C and reacted for 1 h; finally heated to 280 °C and reacted for 2 h to obtain a block copolymer.

[0084] S3. At 280 °C, 4-fluorobenzophenone (0.02 mol) was added for end-capping for 0.5 h and then poured out. The crude product was crushed and washed by refluxing with acetone and deionized water for several times until the impurities such as diphenyl sulfone and inorganic salts in the product were completely removed to obtain a powdery product, and then it was extruded, granulated, and injection-molded, and its performance was evaluated.

[0085] In this example, the molar ratio of the total molar amount of bisphenol fluorene and aromatic diol to the molar amount of the dihalodiphenyl ketone is 1:1; the molar ratio of the aromatic diol to bisphenol fluorene is 1:0.11; The molar ratio of the total molar amount of bisphenol fluorene and aromatic diol to the molar amount of the alkali metal carbonate is 1:1.05; The molar ratio of sodium carbonate to potassium carbonate is 1:0.5; The dosage ratio of the end-capping agent to the total molar amount of bisphenol fluorene and aromatic diol is 0.02:1.

[0086] Comparative Example 4 The same reaction conditions and preparation method as in Example 1, the difference is that: in this Comparative Example 4, bisphenol fluorene and hydroquinone were added to the reaction system simultaneously for reaction, and the specific steps are as follows: S1. A 2L three-necked flask equipped with a mechanical stirrer, a thermometer, and a water separator was evacuated to vacuum and then filled with high-purity nitrogen (≥99.99%). The system was evacuated and filled with nitrogen more than three times to fully replace the air atmosphere in the system with a nitrogen atmosphere, and a certain flow rate of nitrogen was continuously introduced to maintain it. 500 g of diphenyl sulfone (2.29 mol), 4,4'-difluorobenzophenone (1.00 mol), 9,9-bis(4-hydroxyphenyl)fluorene (0.10 mol), and hydroquinone (0.90 mol) were added to the three-necked flask. After heating to 160 °C until all of them melted, sodium carbonate (0.70 mol) and potassium carbonate (0.35 mol) were added, and the reaction was carried out at 160 °C for 1 h; then the temperature was raised to 200 °C and the reaction was carried out for 1 h; then the temperature was raised to 230 °C and the reaction was carried out for 1 h; finally, the temperature was raised to 280 °C and the reaction was carried out for 2 h to obtain a block copolymer.

[0087] S2. At 280 °C, 4-fluorobenzophenone (0.02 mol) was added for end-capping for 0.5 h and then poured out. The crude product was crushed and washed by refluxing with acetone and deionized water for several times until the impurities such as diphenyl sulfone and inorganic salts in the product were completely removed to obtain a powdery product, which was then extruded, granulated, and injection-molded, and its properties were evaluated.

[0088] In this example, the molar ratio of the total molar amount of 9,9-bis(4-hydroxyphenyl)fluorene and aromatic diol to the molar amount of the dihalodiphenyl ketone is 1:1; the molar ratio of the aromatic diol to 9,9-bis(4-hydroxyphenyl)fluorene is 1:0.11; The molar ratio of the total molar amount of 9,9-bis(4-hydroxyphenyl)fluorene and aromatic diol to the alkali metal carbonate is 1:1.05; The molar ratio of sodium carbonate to potassium carbonate is 1:0.5; The dosage ratio of the end-capping agent to the total molar amount of 9,9-bis(4-hydroxyphenyl)fluorene and aromatic diol is 0.02:1.

[0089] The polyaryletherketones prepared in the above examples and comparative examples were subjected to performance tests, and the specific test results are shown in Table 1 below.

[0090] Table 1 Performance test data of polyaryletherketone materials

[0091] As can be seen from Table 1 above, the polyaryletherketone materials prepared by the preparation method described in the present invention in all the examples and comparative examples have higher thermal decomposition temperatures (all greater than 550 °C), corrosion resistance and mechanical properties. At the same time, by adjusting the proportion of bisphenol fluorene introduced, ideal processing properties (melt flow index 8.0 - 30.0 g / 10min) can be imparted to the material. The preparation method described in the present invention introduces bisphenol fluorene as a block copolymerization monomer in the traditional polyaryletherketone preparation method, and a high-quality novel polyaryletherketone material is prepared. In addition, compared with the traditional polyaryletherketone, the preparation method described in the present invention has obvious advantages in terms of energy consumption and has high industrial production and commercial application value. Figure 2 It is the TGA curve of the polyaryletherketone prepared in Example 1. From Figure 2 it can be seen that the polyaryletherketone product prepared by this method has extremely high thermal stability and can meet the use under various harsh conditions.

[0092] Through the data comparison of Example 1, Example 4, and Example 5, it can be seen that due to the large steric hindrance effect of bisphenol fluorene, the activity becomes poor, and sodium carbonate with weak alkalinity is not sufficient to react fully with fluoro ketone, thus affecting the molecular weight of the product and ultimately affecting the overall performance of the product. By introducing an appropriate amount of potassium carbonate with higher activity for catalysis, bisphenol fluorene can form salts more fully and thoroughly in the early prepolymerization stage, ensuring that when hydroquinone is introduced, a regular block main chain structure can be formed, guaranteeing the comprehensive performance of the product.

[0093] Through the data comparison of Example 1 to Example 3, it can be seen that as the dosage of bisphenol fluorene increases, the tensile strength, modulus, and corrosion resistance of the product all increase to a certain extent, indicating the feasibility of introducing bisphenol fluorene as the second phenolic for block copolymerization with fluoro ketone proposed in the present invention. By comparing the measured melt index of the product with the currently commercially available standard products, it can be found that by adjusting the introduction amount of bisphenol fluorene, adjusting the processing temperature (350 - 380 °C) and screw speed (60 - 80 rpm), efficient injection molding of the material can be achieved, having potential industrial value.

[0094] Through the data comparison of Example 1 and Comparative Example 1, it can be seen that if bisphenol fluorene monomer is not introduced, the corrosion resistance and mechanical properties of the obtained polyaryletherketone material will become poor because the rigid chain structure of bisphenol fluorene can restrict the thermal movement of molecular chains and impart high strength and modulus to the product. At the same time, the hydrophobic group of the fluorene ring can reduce the penetration of solvent molecules into the polymer chain, significantly improving its stability in acids, alkalis, and organic solvents. Figure 1 It is the comparison of the tensile curves of the polyaryletherketone products of Example 1 and Comparative Example 1. From Figure 1It can be seen that the introduction of bisphenol fluorene will greatly improve the mechanical properties of the product, endowing the material with higher tensile strength and modulus, while the elongation at break will decrease. The mechanical properties of the final product can be adjusted by adjusting the proportion of bisphenol fluorene introduced according to the performance requirements of the product.

[0095] From the comparison of the data of Example 1 and Comparative Example 2, it can be seen that if bisphenol fluorene is used entirely, although there are obvious improvements in the mechanical properties, corrosion resistance and thermal stability of the product, it will also increase the viscosity of the product and make processing more difficult. Therefore, it is necessary to adjust the proportion of bisphenol fluorene introduced to retain part of hydroquinone as the "soft segment" to ensure the product performance and have certain processability while meeting the product performance requirements.

[0096] From the comparison of the data of Example 1 and Comparative Example 3, it can be seen that adding hydroquinone in batches can effectively alleviate problems such as insufficient reaction caused by different monomer reaction activities, making the arrangement of the two structural units in the main chain structure more regular, thus forming a complete block copolymer network and endowing the material with higher mechanical properties and chemical corrosion resistance.

[0097] From the comparison of the data of Example 1 and Comparative Example 4, it can be seen that due to the influence of large steric hindrance groups, the reaction activity of hydroquinone is much higher than that of bisphenol fluorene. If both are added simultaneously at the beginning of the reaction, it will be difficult for bisphenol fluorene to react fully and block into the main chain structure, ultimately resulting in poor overall performance of the product and failing to achieve the expected effect.

[0098] The technical features of the above embodiments can be combined arbitrarily. For the sake of concise description, not all possible combinations of the technical features in the above embodiments are exhausted. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0099] For those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. The protection scope of the present invention shall be subject to the appended claims.

Claims

1. A preparation method of polyaryletherketone, characterized in that, The preparation method is as follows: S1. Under an inert gas condition, add a dihalodibenzophenone and a bisphenol fluorene into a solvent and mix them evenly, then add an alkali metal carbonate, and carry out a reaction under heating conditions to obtain an oligomer; S2. Add an aromatic diol into the system of step S1 in batches and carry out a programmed temperature rise reaction to obtain a block copolymer; S3. Add a capping agent into the system for a capping reaction, and after the reaction is completed, carry out post-treatment to obtain a polyaryletherketone.

2. The preparation method of a polyaryletherketone according to claim 1, wherein The dihalodibenzophenone is at least one of 2,4'-difluorobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, and 4,4'-dibromobenzophenone; The aromatic diol is at least one of hydroquinone, resorcinol, biphenol, bisphenol A, and phenolphthalein.

3. The preparation method of a polyaryletherketone according to claim 1, wherein The molar ratio of the total molar amount of the bisphenol fluorene and the aromatic diol to the dihalodibenzophenone is 1:(0.95 - 1.15); the molar ratio of the aromatic diol to the bisphenol fluorene is 1:(0.1 - 0.8).

4. The preparation method of a polyaryletherketone according to claim 1, wherein, The molar ratio of the total molar amount of the bisphenol fluorene and the aromatic diol to the alkali metal carbonate is 1:(0.98 - 1.30); The alkali metal carbonate is at least one of potassium carbonate, sodium carbonate, and cesium carbonate.

5. The preparation method of a polyaryletherketone according to claim 4, characterized in that, The alkali metal carbonate is a combination of sodium carbonate and potassium carbonate, and the molar ratio of sodium carbonate to potassium carbonate is 1:(0.01 - 0.5).

6. The preparation method of a polyaryletherketone according to claim 1, characterized in that, The solvent is any one of sulfolane, N,N-dimethylformamide, N,N-dimethylacetamide, diphenyl sulfone, dimethyl sulfoxide, and N-methylpyrrolidone.

7. The preparation method of a polyaryletherketone according to claim 1, characterized in that, The capping agent is at least one of 4-fluorobenzophenone, 4-chlorobenzophenone, and 4-fluorobiphenyl; The dosage ratio of the capping agent to the total molar amount of the bisphenol fluorene and the aromatic diol is (0.01 - 0.05):

1.

8. The preparation method of a polyaryletherketone according to claim 1, characterized in that In step S1, the reaction temperature is 150 - 180 °C and the reaction time is 0.5 - 2 h.

9. The preparation method of a polyaryletherketone according to claim 1, wherein, In step S2, the aromatic diol is added to the reaction system in three batches. After the first batch of the aromatic diol is added to the system, the temperature is raised to 180 - 230 °C and the reaction is carried out for 0.5 - 2 h; after the second batch of the aromatic diol is added to the system, the temperature is raised to 230 - 270 °C and the reaction is carried out for 0.5 - 2 h; after the third batch of the aromatic diol is added to the system, the temperature is raised to 270 - 300 °C and the reaction is carried out for 0.5 - 2 h.

10. The preparation method of a polyaryletherketone according to claim 1, characterized in that, In step S3, the post-treatment operation method is: after the reaction is completed, pour the product into cold water for cooling and solidification, take the solid, crush it, wash it, and dry it to obtain the polyaryletherketone product.

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