Bisphenol a type haloketone monomer, polyaryletherketone resin and preparation method and application thereof
Polyaryletherketone resin with excellent mechanical properties and thermal stability was prepared by polymerizing bisphenol A type halogen ketone monomers with halogen ketone monomers. This solved the problems of poor flowability and insufficient mechanical properties of existing resins, and enabled efficient processing and high-end applications.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HUITONG NEW MATERIALS (SHANGHAI) CO LTD
- Filing Date
- 2026-03-13
- Publication Date
- 2026-06-23
AI Technical Summary
Existing polyaryletherketone resins have poor flowability and insufficient mechanical properties during processing, which affects the expansion of their high-end applications.
Polyaryletherketone resin consisting of linearly randomized structural units 1 and 2 was prepared by polymerizing bisphenol A type halogen ketone monomers with halogen ketone monomers, phenolic monomers and salt-forming agents under an inert atmosphere and controlling the molar ratio and end-capping reaction.
The prepared polyaryletherketone resin has excellent mechanical properties, crystallinity, and thermal stability, and combines flexibility and rigidity, which improves melt flowability and makes it suitable for injection molding and extrusion processing, thereby improving production efficiency.
Smart Images
Figure CN122255452A_ABST
Abstract
Description
[0001] This application claims priority to Chinese patent application 202512032575.2, filed on 2025 / 12 / 30. The entire contents of the aforementioned Chinese patent application are incorporated herein by reference. Technical Field
[0002] This invention relates to a bisphenol A type haloketone monomer, a polyaryletherketone resin, its preparation method, and its application. Background Technology
[0003] Polyaryl ether ketone (PAEK) resins, such as polyether ether ketone (PEEK), are widely used in the aerospace, electronics, electrical, and automotive industries due to their excellent mechanical properties, thermal stability, and chemical resistance. However, the high crystallinity of PEEK leads to problems such as poor flowability and molding difficulties during processing. Current technologies mostly improve resin processability by introducing flexible bisphenol units or biphenyl to reduce crystallinity, but this often affects its mechanical properties.
[0004] Traditional methods for synthesizing polyaryletherketone (PLEK) resins typically employ ternary copolymerization techniques. A classic example is the introduction of bisphenol A monomer, followed by ternary copolymerization with 4,4'-difluorobenzophenone and hydroquinone to synthesize a PLEK resin with a semi-flexible structure (e.g., those disclosed in Chinese patent applications CN102532441B and CN105418910A). This method directly reacts bisphenol A, hydroquinone, and fluoroketone together. While this allows for adjustment of the polymer's crystallinity, the resulting resin often exhibits excessively long flexible segments of bisphenol A, forming long amorphous blocks. This leads to a decrease in the resin's mechanical strength, limiting its expansion into high-end applications. Summary of the Invention
[0005] The technical problem to be solved by this invention is to overcome the defect of poor mechanical strength of polyaryletherketone resins prepared by existing technology, and to provide a bisphenol A type haloketone monomer, a polyaryletherketone resin, its preparation method, and its application. The polyaryletherketone resin prepared using this bisphenol A type haloketone monomer has better mechanical properties, as well as better thermal stability and crystallinity.
[0006] The present invention solves the above-mentioned technical problems through the following technical solution:
[0007] The present invention also provides a polyaryletherketone resin, which is:
[0008] A linear polymer composed of structural unit 1, or
[0009] Polymers composed of linearly random arrangement of structural unit 1 and structural unit 2:
[0010] -R1-A-, structural unit 1;
[0011] -R2-A-, Structural Unit 2;
[0012] Wherein, A is 1'4-phenyldioxy, 1'3-phenyldioxy, or 4'4-biphenyldioxy;
[0013] Wherein, R1 is , , , or ;
[0014] Wherein, R2 is independently defined in different structural units 2. , or ;
[0015] Among them, the end capping base connected to R1 or R2 is H, and the end capping base connected to A is independently defined in different structural units 2. , or X is either F or Cl.
[0016] In this invention, "independently present in different structural units 2" means that in the structural unit 2 of the polyaryletherketone resin, there may be one or more R2 or end-capping groups connected to A.
[0017] In this invention, in the polymer composed of structural unit 1 and structural unit 2 arranged linearly and randomly, the molar ratio of structural unit 1 and structural unit 2 can be (0.1-0.5):(0.01-0.8), for example 0.1:0.8 or 0.3:0.4, preferably (0.3-0.5):(0.01-0.4).
[0018] In this invention, the number average molecular weight of the polyaryletherketone resin can be 20,000-40,000, preferably 30,000-39,000, for example 30468, 36168 or 38943.
[0019] In this invention, the molecular weight distribution index of the polyaryletherketone resin can be 1.8-3.0, preferably 1.8-2, for example 1.97, 1.96 or 1.86.
[0020] The present invention also provides a bisphenol A type haloketone monomer having the structure of Formula I:
[0021] Formula I;
[0022] Wherein, R3 and R4 are , , or ;
[0023] Alternatively, R3 is R4 is ;
[0024] X is either F or Cl.
[0025] The present invention also provides a method for preparing polyaryletherketone resin as described above, comprising the following steps: under an inert atmosphere, in a solvent, in the presence or absence of a halogen ketone monomer, a bisphenol A type halogen ketone monomer, a phenolic monomer and a salting agent as shown in Formula I are subjected to a polymerization reaction, followed by a capping reaction with a halogen ketone monomer as a capping agent, to obtain the resin.
[0026] In this invention, the phenolic monomer may be hydroquinone, resorcinol, or biphenyl.
[0027] In this invention, the halogen ketone monomer may be one or more of 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 3,4'-difluorobenzophenone, 3,4'-dichlorobenzophenone, 4,4'-difluorotriphenyldione, and 4,4'-dichlorotriphenyldione, for example, 4,4'-difluorobenzophenone.
[0028] In this invention, the molar ratio of the bisphenol A type halogen ketone monomer, the halogen ketone monomer, and the phenolic monomer can be (0.05-0.5):(0-0.9):(0.5-0.95), preferably (0.1-0.5):(0-0.8):(0.5-0.9), for example 0.1:0.8:0.9, 0.3:0.4:0.7 or 0.5:0:0.5, and most preferably (0.3-0.5):(0-0.4):(0.5-0.7).
[0029] In this invention, the type and content of the salt-forming agent can be selected according to conventional methods in the art. Specifically, the salt-forming agent is preferably an alkali metal carbonate, such as sodium carbonate and / or potassium carbonate. When the salt-forming agent is sodium carbonate and potassium carbonate, the mass ratio of sodium carbonate to potassium carbonate is preferably (10-20):(0-1). The molar ratio of the salt-forming agent to the phenolic monomer can be (1-1.5):1, more preferably (1-1.2):1, for example 1.1:1, 1.2:1, or 1.14:1.
[0030] In this invention, the type and content of the solvent can be selected according to conventional methods in the art. Specifically, the solvent is preferably a sulfone solvent, such as diphenyl sulfone and / or sulfolane. The molar ratio of the total molar number of the bisphenol A type haloketone monomer and the phenolic monomer to the molar ratio of the solvent is preferably 1:(3-6), more preferably 1:(3.5-5), for example 1:4.1.
[0031] In this invention, the halogen ketone monomer used as the capping agent may be one or more of 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 3,4'-difluorobenzophenone, 3,4'-dichlorobenzophenone, 4,4'-difluorotriphenyldione, and 4,4'-dichlorotriphenyldione, for example, 4,4'-difluorobenzophenone.
[0032] In this invention, the ratio of the molar number of the capping agent to the total molar number of the bisphenol A type halogen ketone monomer and the halogen ketone monomer is (0.01-0.1):1, preferably (0.02-0.05):1, for example 0.022:1, 0.028:1 or 0.04:1.
[0033] In this invention, prior to the polymerization reaction, it is preferable to uniformly mix the bisphenol A type halogen ketone monomer, the halogen ketone monomer, the solvent, the phenolic monomer, and the salt-forming agent. The mixing is preferably carried out at room temperature, for example, at 25-30°C. Prior to the mixing, it is preferable to further purge the air with nitrogen to create an inert atmosphere. The purge time is preferably 15-30 minutes. The particle size of the uniformly mixed material can be 200-300 mesh. The uniform mixing can be in a solid state or in a solution state. Solid state mixing means first mixing the bisphenol A type halogen ketone monomer, the halogen ketone monomer, the phenolic monomer, and the salt-forming agent, and then adding the solvent. Solution state mixing means first mixing any one of the raw materials with the solvent, and then adding the other raw materials.
[0034] In this invention, the polymerization reaction can be carried out under normal pressure.
[0035] In this invention, the temperature of the polymerization reaction can be as conventional in the art, generally 200-320℃. Preferably, a gradient heating method can be used. The number of gradient heating can be 2-4, for example 3.
[0036] In a preferred embodiment, the number of gradients in the gradient heating is 3, which are denoted as the first gradient, the second gradient, and the third gradient, respectively, wherein the temperature of the first gradient is less than the temperature of the second gradient and the temperature of the third gradient.
[0037] The temperature of the first gradient is preferably 140-210℃, for example 140℃; the holding time under the first gradient can be 1-2h, preferably 1 or 1.5h; the heating rate from room temperature to the temperature of the first gradient can be 1~5℃ / min, for example 2℃ / min.
[0038] The temperature of the second gradient is preferably 250-280℃, for example 250℃; the holding time under the second gradient can be 2-4h, preferably 3h; the heating rate from the temperature of the first gradient to the temperature of the second gradient can be 1~5℃ / min, for example 3.67 or 4℃ / min.
[0039] The temperature of the third gradient is preferably 300-315℃, for example, 310℃. The holding time under the third gradient can be 0.5-2h, preferably 1h; the heating rate from the temperature of the second gradient to the temperature of the third gradient can be 1~5℃ / min, for example, 2℃ / min.
[0040] In this invention, the temperature of the end-capping reaction is the same as the temperature of the third gradient, which can be 300-315℃, for example, 310℃. The duration of the end-capping reaction can be 0.5-2h, preferably 0.5h.
[0041] In this invention, the inert atmosphere can be conventional in the art, such as a nitrogen atmosphere.
[0042] In this invention, after the end-capping reaction, post-processing steps such as cooling, pulverizing, washing, filtering, and drying may conventionally be included. The washing solvent can be conventional, for example, acetone, ethanol, and water sequentially. The washing time can be 24 hours. The drying temperature can be 110-130°C, for example, 120°C. The drying time can be selected according to conventional methods in the art, generally greater than 12 hours.
[0043] The present invention also provides a method for preparing bisphenol A type haloketone monomer as described above, which includes the following steps: reacting bisphenol A, haloketone monomer and salting agent in a solvent under an inert atmosphere to obtain the product.
[0044] In this invention, the halogenated ketone monomer may be 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 3,4'-difluorobenzophenone, 3,4'-dichlorobenzophenone, 4,4'-difluorotriphenyldione, or 4,4'-dichlorotriphenyldione.
[0045] In this invention, the type and content of the salt-forming agent can be selected according to conventional methods in the art. Specifically, the salt-forming agent is preferably an alkali metal carbonate, such as sodium carbonate and / or potassium carbonate. When the salt-forming agent is sodium carbonate and potassium carbonate, the mass ratio of sodium carbonate to potassium carbonate is preferably (10-20):(0-1).
[0046] In this invention, the molar ratio of bisphenol A, the haloketone monomer and the salting agent can be 1:(2-5):(1.1-2), preferably 1:(2.2-4):(1-1.5), for example 1:2.2:1.2 or 1:3:1.2.
[0047] In this invention, preferably, the bisphenol A, the haloketone monomer, and the salt-forming agent are first mixed, and then mixed with a solvent. Conventionally, mixing is preferably carried out under stirring conditions. The stirring speed is preferably 100 rpm.
[0048] In this invention, the solvent can be any conventional solvent in the art, preferably a nitrogen-containing heterocyclic solvent, such as N-methyl-2-pyrrolidone (NMP) or an amide solvent. The amide solvent is preferably N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMAc).
[0049] In this invention, the inert atmosphere can be conventional in the art, such as a nitrogen atmosphere.
[0050] In this invention, the reaction temperature can be 100-180℃, preferably 140℃.
[0051] In this invention, the reaction time can be 2-5 hours, preferably 3 or 4 hours. The endpoint of the reaction can be detected by TLC plate testing.
[0052] In this invention, after the reaction is completed, post-processing operations may conventionally be included, which may specifically include precipitation, washing, filtration and drying.
[0053] The solvent used during precipitation can be methanol.
[0054] The present invention also provides an application of the polyaryletherketone resin as described above in the preparation of plastic products.
[0055] The positive and progressive effects of this invention are as follows:
[0056] (1) The polyaryletherketone resin of the present invention avoids the defects of low mechanical properties in the prior art, and has better mechanical properties, crystallinity, glass transition temperature and melting point, and can achieve a balance between flexibility and rigidity; it has better melt flowability, making it suitable for injection molding, extrusion and other processing processes, which can significantly improve production efficiency.
[0057] (2) In the preparation method of the present invention, the content of bisphenol A structural unit in polyarylether ketone resin can be precisely adjusted by controlling the molar ratio of bisphenol A type halogen ketone monomer to halogen ketone monomer, thereby controlling the polyarylether crystallinity, glass transition temperature, melting point and other properties of the resin, especially its processability, which has better controllability. Attached Figure Description
[0058] Figure 1 The infrared spectrum of the bisphenol A type haloketone monomer prepared in Example 1 is shown.
[0059] Figure 2 The image shows the infrared spectrum of the polyaryletherketone resin prepared in Example 1.
[0060] Figure 3 The NMR spectrum is shown for the bisphenol A type haloketone monomer obtained in Example 1. Detailed Implementation
[0061] The present invention will be further illustrated by way of embodiments below, but the present invention is not limited to the scope of the embodiments described herein.
[0062] Example 1: A method for preparing a bisphenol A type difluorodione monomer
[0063] Take three 3000 mL reaction vessels, equip them with heating jackets, top-mounted stirrers, three-way mercury thermometers, etc., and construct a reaction device. Stable nitrogen flow of 3L / min is introduced through the air inlet of the three-way mercury thermometer.
[0064] 228.3 g (1 mol) of bisphenol A (particle size less than 200 mesh), 480.0 g (2.2 mol) of 4,4'-difluorobenzophenone, and 127.2 g (1.2 mol) of sodium carbonate in powder form were added to a reactor, and the stirrer was started at 100 rpm to thoroughly mix the materials, ensuring the particle size of the mixture was less than 200 mesh. During this process, a nitrogen gas flow was maintained to ensure sufficient gas replacement. 2000 mL of NMP was added, and the reaction was carried out at 140 °C for 3 hours under nitrogen protection to ensure complete reaction of bisphenol A with 4,4'-difluorobenzophenone. The reaction endpoint could be detected by TLC. After the reaction, the product was poured into a large amount of methanol (5000 mL) and stirred thoroughly. The precipitate was further slurried with deionized water, filtered, and dried to obtain the bisphenol A-type difluorodione monomer.
[0065] Example 2: A polyaryletherketone resin and its preparation method
[0066] A four-port split 2000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.
[0067] 62.5 g (0.1 mol) of bisphenol A type difluorodione monomer (particle size less than 200 mesh), 174.6 g (0.8 mol) of 4,4'-difluorobenzophenone, 99.1 g (0.9 mol) of hydroquinone, 0.9 kg (4.1 mol) of diphenyl sulfone and 114.5 g (1.1 mol) of sodium carbonate in powder form were added to the reactor, and the agitator was started at 100 rpm to thoroughly stir the mixture to obtain a mixture with a particle size less than 200 mesh; during this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.
[0068] Under normal pressure, the reactor was uniformly heated from room temperature to 140°C for 1 hour and held at that temperature for 1.5 hours; then, after 30 minutes, the temperature was further increased to 250°C and held for 4 hours; finally, the temperature was increased to 310°C for 30 minutes and held for 1 hour. Finally, 5 g (0.02 mol) of 4,4'-difluorobenzophenone was added to the reaction system, and the mixture was capped at 310°C for 30 minutes to complete the reaction.
[0069] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 500 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 24 h in sequence. The sample was then dried at 120 °C overnight to obtain the PAEK resin sample.
[0070] Example 3: A polyaryletherketone resin and its preparation method
[0071] A four-port split 2000 mL reactor is equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400℃), a water separator, and a condenser to construct the reaction apparatus. A nitrogen gas flow of 3 L / min is stably introduced through the inlet of the three-way mercury thermometer.
[0072] 187.4 g (0.3 mol) of bisphenol A type difluorodione monomer (particle size less than 200 mesh), 87.3 g (0.4 mol) of 4,4'-difluorobenzophenone, 77.1 g (0.7 mol) of hydroquinone, 0.9 kg (4.1 mol) of diphenyl sulfone and 89.0 g (0.8 mol) of sodium carbonate in powder form were added to the reactor, and the agitator was started at 100 rpm to thoroughly stir the mixture to obtain a mixture with a particle size less than 200 mesh; during this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.
[0073] Under normal pressure, the reactor was uniformly heated from room temperature to 140 °C for 1 h and held at that temperature for 1.5 h; then, after 30 min, the temperature was further increased to 250 °C and held for 4 h; finally, after 30 min, the temperature was increased to 310 °C and held for 1 h. Finally, 5 g (0.02 mol) of 4,4'-difluorobenzophenone was added to the reaction system, and the mixture was capped at 310 °C for 30 min to complete the reaction.
[0074] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 500 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h respectively. The sample was then dried at 120 °C overnight to obtain the PAEK resin sample.
[0075] Example 4: A polyaryletherketone resin and its preparation method
[0076] A four-port split 2000 mL reactor was constructed, equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400 ℃), a water separator, and a condenser. A nitrogen gas flow of 3 L / min was stably introduced through the inlet of the three-way mercury thermometer.
[0077] 312.3 g (0.5 mol) of bisphenol A type difluorodione monomer (particle size less than 200 mesh), 55.1 g (0.5 mol) of hydroquinone, 0.9 kg (4.1 mol) of diphenyl sulfone and 63.6 g (0.6 mol) of sodium carbonate in powder form were added to the reactor, and the agitator was started at 100 rpm to thoroughly stir the mixture to obtain a mixture with a particle size less than 200 mesh; during this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.
[0078] Under normal pressure, the reactor was uniformly heated from room temperature to 140 °C for 1 h and held at that temperature for 1.5 h; then, after 30 min, the temperature was further increased to 250 °C and held for 4 h; finally, after 30 min, the temperature was increased to 310 °C and held for 1 h. Finally, 5 g (0.02 mol) of 4,4'-difluorobenzophenone was added to the reaction system, and the mixture was capped at 310 °C for 30 min to complete the reaction.
[0079] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 500 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h respectively. The sample was then dried at 120 °C overnight to obtain the PAEK resin sample.
[0080] Comparative Example 1: A polyaryletherketone resin and its preparation method
[0081] A four-port split 2000 mL reactor was constructed, equipped with a heating jacket, a top-mounted stirrer, a three-way mercury thermometer (maximum measurement value 400 ℃), a water separator, and a condenser. A nitrogen gas flow of 3 L / min was stably introduced through the inlet of the three-way mercury thermometer.
[0082] 114.1 g (0.5 mol) of bisphenol A, 218.2 g (1 mol) of 4,4'-difluorobenzophenone, 55.1 g (0.5 mol) of hydroquinone, 0.9 kg (4.1 mol) of diphenyl sulfone and 127.2 g (1.2 mol) of sodium carbonate in powder form were added to the reactor, and the agitator was started at 100 rpm to thoroughly stir the mixture to obtain a mixture with a particle size of less than 200 mesh. During this period, a nitrogen gas flow was maintained to ensure sufficient gas replacement.
[0083] Under normal pressure, the reactor was uniformly heated from room temperature to 140 °C for 1 h and held at that temperature for 1.5 h; then, after 30 min, the temperature was further increased to 250 °C and held for 4 h; finally, the temperature was increased to 310 °C for 30 min and held for 1 h. Finally, 5 g of 4,4'-difluorobenzophenone was added to the reaction system, and the mixture was kept at 310 °C for 30 min to seal the reaction, completing the reaction.
[0084] After the reaction was complete, the material was poured into a stainless steel pan, cooled and solidified, then crushed. 500 g of the sample was placed in a Soxhlet extractor and washed with acetone, ethanol and water for 12 h respectively. The sample was then dried at 120 °C overnight to obtain the PAEK resin sample.
[0085] Verification Example 1
[0086] 1. The bisphenol A type difluorodione monomer obtained in Example 1 was subjected to infrared spectroscopy. The results are as follows: Figure 1 As shown. The bisphenol A type difluorodione monomer obtained in Example 1 was subjected to NMR analysis. The results are as follows. Figure 3 As shown.
[0087] 2. The polyaryletherketone resins prepared in Examples 2-4 were subjected to infrared spectroscopy. The results are as follows: Figure 2 As shown.
[0088] Example 1
[0089] 1. The number-average molecular weight and molecular weight distribution of the polyaryletherketone resins prepared in Examples 2-4 and Comparative Example 1 were tested respectively.
[0090] The molecular weight and molecular weight distribution were determined by gel permeation chromatography (GPC) with test conditions in accordance with GB / T 21863-2008 (the eluent was tetrahydrofuran, and the standard sample of narrow-distribution polystyrene was used for calibration).
[0091] The test results are shown in Table 1.
[0092] Table 1
[0093]
[0094] The molar ratios of structural unit 1 and structural unit 2 of the polyaryletherketone resins prepared in Examples 2-4 and Comparative Example 1 are shown in Table 2.
[0095] Table 2
[0096]
[0097] 2. The polyaryletherketone resins prepared in Examples 2-4 and Comparative Example 1 were subjected to differential scanning calorimetry (DSC) to test their glass transition temperature (Tg), melting point (Tm), crystallization temperature (Tc), crystallinity, 5% thermogravimetric temperature (TGF-β), and tensile strength. The testing standard was GB / T 19466.
[0098] The glass transition temperature (Tg) refers to the temperature at which the amorphous portion of an amorphous (non-crystalline) polymer or a semi-crystalline polymer transitions from the glassy state to the elastic state.
[0099] Melting point Tm refers to the temperature at which the crystal structure of a crystalline polymer completely disintegrates when heated, transforming from an ordered three-dimensional crystalline state to a disordered viscous flow state.
[0100] Crystallization temperature Tc refers to the temperature at which a polymer transforms from an amorphous or elastic state to a crystalline state during the cooling process.
[0101] The method for testing crystallinity is as follows: The enthalpy of melting (ΔHf) of the polymer sample is obtained through DSC testing, and the formula is: Crystallinity Xc (%) = (ΔHf / ΔHf) 0 The crystallinity of the sample is calculated by multiplying (equilibrium melting enthalpy) / g by 100%.
[0102] 5% thermogravimetric temperature: The polyaryletherketone resins prepared in Examples 2-4 and Comparative Example 1 were placed in a thermogravimetric analyzer (TGA) and the temperature at which the polyaryletherketone resin lost 5% of its mass was recorded at a heating rate of 10°C / min under air atmosphere.
[0103] Tensile strength: According to ISO 527 standard, the tensile strength of the polymer material was measured using a universal testing machine after the standard test specimens were injection molded by an injection molding machine. Each sample was tested 5 times and the average value was taken.
[0104] The test results are shown in Table 3.
[0105] Table 3
[0106]
[0107] Note: In Table 3, the molar ratio of ketone groups, bisphenol A and hydroquinone structural units represents the molar ratio of "bisphenol A type halogen ketone monomers and ketone groups in halogen ketone monomers", bisphenol A structural units and hydroquinone structural units in the raw materials for preparing polyarylether ketone resins.
[0108] Comparing the properties of Examples 2-4 with those of traditional PEEK resin (Tg=143℃, Tm=343℃), the polyaryletherketone resin of the present invention has a higher Tg, thus exhibiting excellent stability. Its relatively lower melting point and crystallinity allow it to maintain excellent mechanical properties while producing resins with better melt flowability, which is beneficial for injection molding, extrusion and other processing technologies, and can significantly improve production efficiency.
[0109] Comparing Examples 2-4 with Comparative Example 1, the polyaryletherketone resin obtained by stepwise polymerization has stronger thermal stability and higher crystallinity than that obtained by direct ternary copolymerization, and therefore its mechanical properties are significantly better.
[0110] While specific embodiments of the present invention have been described above, those skilled in the art should understand that these are merely illustrative examples, and the scope of protection of the present invention is defined by the appended claims. Those skilled in the art can make various changes or modifications to these embodiments without departing from the principles and essence of the present invention, but all such changes and modifications fall within the scope of protection of the present invention.
Claims
1. A polyaryletherketone resin, characterized in that, It is: A linear polymer composed of structural unit 1, or, Polymers composed of linearly random arrangement of structural unit 1 and structural unit 2: -R1-A-, structural unit 1; -R2-A-, Structural Unit 2; Wherein, A is 1'4-phenyldioxy, 1'3-phenyldioxy, or 4'4-biphenyldioxy; Wherein, R1 is , , , or ; Wherein, R2 is independently defined in different structural units 2. , or ; Among them, the end capping base connected to R1 or R2 is H, and the end capping base connected to A is independently defined in different structural units 2. , or X is either F or Cl.
2. The polyaryletherketone resin according to claim 1, characterized in that, The polyaryletherketone resin satisfies one or more of the following conditions: (1) In the polymer of linear random arrangement of structural unit 1 and structural unit 2, the molar ratio of structural unit 1 and structural unit 2 is (0.1-0.5):(0.01-0.8), for example 0.1:0.8 or 0.3:0.4, preferably (0.3-0.5):(0.01-0.4). (2) The number average molecular weight of the polyaryletherketone resin is 20,000-40,000, preferably 30,000-39,000, for example 30468, 36168 or 38943; (3) The molecular weight distribution index of the polyaryletherketone resin is 1.8-3.0, preferably 1.8-2, for example 1.97, 1.96 or 1.
86.
3. A bisphenol A type haloketone monomer, characterized in that, It has the structure of Equation I as follows: Equation I; Wherein, R3 and R4 are , , or ; Alternatively, R3 is R4 is ; X is either F or Cl.
4. A method for preparing the polyaryletherketone resin as described in claim 1 or 2, characterized in that, It includes the following steps: under an inert atmosphere, in a solvent, in the presence or absence of a halogenated ketone monomer, a bisphenol A type halogenated ketone monomer, a phenolic monomer, and a salting agent are polymerized, and then the monomer is capped with a halogenated ketone monomer as a capping agent to obtain the product.
5. The method for preparing the polyaryletherketone resin according to claim 4, characterized in that, The preparation method of the polyaryletherketone resin satisfies one or more of the following conditions: (1) The phenolic monomer is hydroquinone, resorcinol or biphenyl; (2) The halogenated ketone monomer is one or more of 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 3,4'-difluorobenzophenone, 3,4'-dichlorobenzophenone, 4,4'-difluorotriphenyldione and 4,4'-dichlorotriphenyldione, for example 4,4'-difluorobenzophenone; (3) The molar ratio of the bisphenol A type haloketone monomer, the haloketone monomer and the phenolic monomer is (0.05-0.5):(0-0.9):(0.5-0.95), preferably (0.1-0.5):(0-0.8):(0.5-0.9), for example 0.1:0.8:0.9, 0.3:0.4:0.7 or 0.5:0:0.5, and most preferably (0.3-0.5):(0-0.4):(0.5-0.7); (4) The salt-forming agent is an alkali metal carbonate, such as sodium carbonate and / or potassium carbonate; Wherein, when the salt-forming agent is sodium carbonate and potassium carbonate, the mass ratio of sodium carbonate to potassium carbonate is preferably (10-20):(0-1). The preferred molar ratio of the salt-forming agent to the phenolic monomer is (1-1.5):1, more preferably (1-1.2):1, for example 1.1:1, 1.2:1 or 1.14:1; (5) The solvent is a sulfone solvent, such as diphenyl sulfone and / or sulfolane; The molar ratio of the total number of bisphenol A type haloketone monomers and the phenolic monomers to the solvent is preferably 1:(3-6), more preferably 1:(3.5-5), for example 1:4.1; (6) The halogenated ketone monomer used as the capping agent is one or more of 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 3,4'-difluorobenzophenone, 3,4'-dichlorobenzophenone, 4,4'-difluorotriphenyldione and 4,4'-dichlorotriphenyldione, for example 4,4'-difluorobenzophenone; (7) The ratio of the number of moles of the capping agent to the total number of moles of the bisphenol A type halogen ketone monomer and the halogen ketone monomer is (0.01-0.1):1, preferably (0.02-0.05):1, for example 0.022:1, 0.028:1 or 0.04:
1.
6. The method for preparing the polyaryletherketone resin according to claim 4, characterized in that, The preparation method of the polyaryletherketone resin satisfies one or more of the following conditions: (1) Before the polymerization reaction, the bisphenol A type haloketone monomer, haloketone monomer, solvent, phenolic monomer and salting agent are mixed evenly; The mixing is preferably carried out at 25-30°C; Prior to the mixing, it is preferable to perform a step of replacing the air with nitrogen to create an inert atmosphere in the system; the replacement time is preferably 15-30 minutes; and the particle size of the material after uniform mixing is preferably 200-300 mesh. (2) The polymerization reaction temperature is 200-320℃; (3) The temperature of the end-capping reaction is 300-315℃, for example 310℃; (4) The capping reaction time is 0.5-2 hours, for example, 0.5 hours; (5) The inert atmosphere is a nitrogen atmosphere; (6) After the end-capping reaction, the process also includes post-processing steps such as cooling, crushing, washing, filtering and drying; The preferred washing method is to wash with acetone, ethanol and water in sequence; The drying temperature is preferably 110-130℃, for example 120℃.
7. The method for preparing the polyaryletherketone resin according to claim 6, characterized in that, The temperature is increased to the polymerization reaction temperature using a gradient heating method; The number of gradients in the gradient heating is preferably 2-4, for example 3; Preferably, the number of gradients in the gradient heating is 3, which are denoted as the first gradient, the second gradient, and the third gradient, respectively, and the temperature of the first gradient is less than the temperature of the second gradient and the temperature of the third gradient. The temperature of the first gradient is preferably 140-210℃, for example 140℃; the holding time under the first gradient is preferably 1-2h, for example 1 or 1.5h; the heating rate from room temperature to the temperature of the first gradient is preferably 1~5℃ / min, for example 2℃ / min. The temperature of the second gradient is preferably 250-280℃, for example 250℃; the holding time under the second gradient is preferably 2-4h, for example 3h; the heating rate from the temperature of the first gradient to the temperature of the second gradient is preferably 1~5℃ / min, for example 3.67 or 4℃ / min. The temperature of the third gradient is preferably 300-315℃, for example 310℃; the holding time under the third gradient is preferably 0.5-2h, for example 1h; the heating rate from the temperature of the second gradient to the temperature of the third gradient is preferably 1~5℃ / min, for example 2℃ / min.
8. A method for preparing a bisphenol A type haloketone monomer as described in claim 3, characterized in that, It includes the following steps: under an inert atmosphere, in a solvent, bisphenol A, a haloketone monomer and a salt-forming agent are reacted to obtain the product.
9. The method for preparing bisphenol A type haloketone monomers as described in claim 8, characterized in that, The method for preparing the bisphenol A type haloketone monomer satisfies one or more of the following conditions: (1) The halogenated ketone monomer is 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 3,4'-difluorobenzophenone, 3,4'-dichlorobenzophenone, 4,4'-difluorotriphenyldione or 4,4'-dichlorotriphenyldione; (2) The salt-forming agent is an alkali metal carbonate, such as sodium carbonate and / or potassium carbonate; Wherein, when the salt-forming agent is sodium carbonate and potassium carbonate, the mass ratio of sodium carbonate to potassium carbonate is preferably (10-20):(0-1). (3) The molar ratio of the bisphenol A, the haloketone monomer and the salting agent is 1:(2-5):(1.1-2), preferably 1:(2.2-4):(1-1.5), for example 1:2.2:1.2 or 1:3:1.2; (4) The solvent is a nitrogen heterocyclic solvent, such as N-methyl-2-pyrrolidone (NMP) or an amide solvent; The preferred amide solvent is N,N-dimethylformamide (DMF) or N,N-dimethylacetamide (DMAc). (5) The inert atmosphere is a nitrogen atmosphere; (6) The reaction temperature is 100-180℃, preferably 140℃; (7) The reaction time is 2-5 hours, preferably 3 or 4 hours.
10. The use of a polyaryletherketone resin as described in claim 1 or 2 in the preparation of plastic articles.