Polyaryletherketone copolymer and preparation method therefor
Patent Information
- Application Number
- PCT/CN2026/080476
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-02-28
- Filing Date
- 2026-02-28
- Publication Date
- 2026-09-03
Smart Images
Figure CN2026080476_03092026_PF_FP_ABST
Abstract
Description
A polyaryletherketone copolymer and its preparation method Technical Field
[0001] This invention relates to the field of polymer materials technology, and in particular to a polyaryletherketone copolymer and its preparation method. Background Technology
[0002] PEEK is an important high-performance engineering plastic with broad application prospects in aerospace, new energy vehicles, wind power, and other fields. However, PEEK has a high melting point and melt viscosity, which makes it difficult to achieve a uniform effect when impregnated with continuous carbon fibers, thus preventing the production of high-quality continuous carbon fiber reinforced prepreg unidirectional tapes. This technical problem severely restricts the application of PEEK as a substitute for traditional materials in the aforementioned fields.
[0003] In existing technologies, PEEK materials are typically processed using traditional methods such as injection molding and extrusion molding, or by preparing continuous carbon fiber reinforced prepreg unidirectional tapes. These processing methods require high temperature and pressure conditions and rely on specialized equipment and techniques, which not only increases the processing difficulty but also significantly raises production costs. These issues pose both technical and economic challenges to manufacturers and also affect the actual application of products by customers.
[0004] VICTREX-LMPAEK was developed by Vigus Manufacturing Company in the UK to address the above issues. TM Low-melting-point PAEK products, including VICTREXAE 250 unidirectional tape and VICTREXAM 200 wire, while improving processing performance to some extent, utilize resorcinol-based raw materials such as 1,4-benzenediol, 1,2-benzenediol, 1,3-benzenediol, and 4,4′-biphenyl, resulting in a lower glass transition temperature (Tg) of ≤153℃ and higher production costs. Furthermore, while maintaining high-temperature resistance, these products require further optimization of their glass transition temperature (Tg) and other performance indicators. Summary of the Invention
[0005] The purpose of this invention is to provide a polyaryletherketone copolymer and its preparation method to solve the technical problems of high melting point and high viscosity of PEEK in the prior art.
[0006] To achieve the above-mentioned objective, the present invention provides a polyaryletherketone copolymer comprising: a repeating unit of Formula I, a repeating unit of Formula II, and a terminal unit, wherein the molar ratio of the repeating unit of Formula I to the repeating unit of Formula II is 55:45 to 95:5;
[0007] The repeating unit of Equation II is:
[0008] The repeat unit of Formula I includes:
[0009] Optionally, the repeat unit of Formula I includes 50 to 90 mol% of repeat units of Formula III and 10 to 50 mol% of repeat units of Formula IV and independent units of Formula V, wherein:
[0010] The repeat unit of Formula III is:
[0011] The repeat unit of Formula IV is:
[0012] The independent unit of Formula V is an RnPEEK structural unit containing a naphthalenediol structure, the naphthalenediol being selected from at least one of 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,3-naphthalenediol, and 2,7-naphthalenediol.
[0013] Optionally, the repeat unit of Formula I includes 65 to 90 mol% of repeat units of Formula III and 10 to 35 mol% of repeat units of Formula IV, independent units of Formula V, or a mixture thereof.
[0014] Optionally, the repeat unit of Formula I includes 80 to 90 mol% of repeat units of Formula III and 10 to 20 mol% of repeat units of Formula IV, independent units of Formula V, or a mixture thereof.
[0015] Optionally, the repeat unit of Formula I includes 10 to 50 mol% of repeat units of Formula III and 50 to 90 mol% of independent units of Formula V, the repeat unit of Formula III being:
[0016] The independent unit of Formula V is an RnPEEK structural unit containing a naphthalenediol structure, the naphthalenediol being selected from at least one of 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 2,3-naphthalenediol, and 2,7-naphthalenediol.
[0017] Optionally, the molar ratio of the repeat unit of Formula I to the repeat unit of Formula II is 90:10 to 80:20.
[0018] Optionally, the end group of the copolymer is an -OH group or an -F group.
[0019] Optionally, the end group of the copolymer includes
[0020] The present application also provides a method for preparing the polyaryletherketone copolymer as described above, comprising:
[0021] polycondensing a mixture of 4,4'-difluorobenzophenone and a dihydroxy compound;
[0022] An end-capping agent is added to the reaction system, wherein the end-capping agent is selected from at least one of phenol, 4-tert-butylphenol or 4,4'-difluorobenzophenone;
[0023] The mixture of dihydroxy compounds includes 1,4-dihydroxynaphthalene or 1,5-dihydroxynaphthalene, and at least one of 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl, 1,3-dihydroxybenzene or 1,2-dihydroxybenzene;
[0024] The molar content of the 1,4-dihydroxynaphthalene or 1,5-dihydroxynaphthalene is 10% to 50% of the total molar amount of the dihydroxy compound mixture.
[0025] Optionally, the polycondensation reaction is carried out under alkaline conditions, which are achieved by adding an alkaline compound selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide.
[0026] Optionally, the molar ratio of the mixture of 4,4'-difluorobenzophenone and the dihydroxy compound is from 1.005:1 to 1.05:1.
[0027] The polyaryletherketone copolymer provided by this invention can effectively reduce the melting point while maintaining a high glass transition temperature by introducing naphthol structural units into the molecular structure, thereby reducing the processing temperature, improving processing performance, and making it easier to impregnate with continuous carbon fibers, which is beneficial for preparing high-quality continuous carbon fiber reinforced prepreg unidirectional tape.
[0028] By combining structural units in specific proportions and using end-capping agents, the molecular weight distribution of the polymer can be further optimized, its thermal stability and mechanical properties can be improved, and the reaction rate and product yield can be increased by carrying out polycondensation under alkaline conditions, thereby reducing production costs. Attached Figure Description
[0029] Figure 1 is a schematic diagram of the rheological properties of Embodiments 7 and 8 of the present invention compared with Victrex PEEK 150G and Victrex PEEK 450G;
[0030] Figure 2 is a schematic diagram of the rheological properties of embodiments 7 and 8 of the present invention compared with Victrex PEEK 150G, Victrex PEEK 450G and Victrex PEEK 650G. Detailed Implementation
[0031] The present invention will now be described in more detail, illustrating preferred embodiments thereof. It should be understood that those skilled in the art can modify the invention described herein while still achieving its advantageous effects. Therefore, the following description should be understood as being of general knowledge to those skilled in the art and is not intended to limit the invention.
[0032] The invention is described in more detail by way of example in the following paragraphs. The advantages and features of the invention will become clearer from the following description.
[0033] The present invention provides a polyaryletherketone copolymer comprising: a repeating unit of formula I, a repeating unit of formula II, and a terminal unit, wherein the molar ratio of the repeating unit of formula I to the repeating unit of formula II is 55:45 to 95:5.
[0034] The repeating unit of formula I includes:
[0035] The repeating unit of Equation II is:
[0036] The Formula I repeating unit comprises 50 to 90 mol% of Formula III repeating units and 10 to 50 mol% of Formula IV repeating units and Formula V independent units, wherein:
[0037] The repeating unit of Equation III is:
[0038] The IV repeating unit is:
[0039] The independent unit of formula V is an RnPEEK structural unit containing a naphthodiol structure, wherein the naphthodiol is selected from at least one of 1,4-naphthodiol, 1,5-naphthodiol, 1,6-naphthodiol, 2,3-naphthodiol and 2,7-naphthodiol.
[0040] In a preferred embodiment, the Formula I repeating unit comprises 65 to 90 mol% of Formula III repeating units and 10 to 35 mol% of Formula IV repeating units, Formula V independent units, or combinations thereof.
[0041] In a more preferred embodiment, the Formula I repeating unit comprises 80 to 90 mol% of Formula III repeating units and 10 to 20 mol% of Formula IV repeating units, Formula V independent units, or mixtures thereof. This proportioning can better balance the melting point and temperature resistance of the material.
[0042] In another specific embodiment, the copolymer may be a copolymer that does not include the IV repeating unit.
[0043] That is, the formula I repeating unit includes 10 to 50 mol% of the formula III repeating unit and 50 to 90 mol% of the formula V independent unit, wherein the formula III repeating unit is:
[0044] The independent unit of formula V is an RnPEEK structural unit containing a naphthodiol structure, wherein the naphthodiol is selected from at least one of 1,4-naphthodiol, 1,5-naphthodiol, 1,6-naphthodiol, 2,3-naphthodiol and 2,7-naphthodiol.
[0045] It should be noted that Formula I does not provide information on whether the ether bonds of the -O-Ph-O- portion are arranged in para, meta, or ortho configurations, while Formulas III, IV, and V do specify this, as do all other configurations within the repeating unit.
[0046] Furthermore, the molar ratio of the repeating unit of Formula I and the repeating unit of Formula II is 60:40 to 90:10, preferably 70:30 to 90:10, and more preferably 80:20 to 90:10.
[0047] In a more preferred embodiment, the molar ratio of the repeating unit of Formula I and the repeating unit of Formula II is 90:10 to 80:20.
[0048] Furthermore, the terminal groups of the copolymer are -OH groups or -F groups.
[0049] Furthermore, the terminal groups of the copolymer include:
[0050] Specifically, in the copolymer provided in this embodiment, the terminal unit is the same as the repeating unit of the copolymer but terminated with a terminal -OH or -F portion.
[0051] In addition to terminal units that are identical to the repeating units of the copolymer but terminated with a terminal -OH or -F portion, the terminal units also include As the end unit.
[0052] In this embodiment, the end unit helps to improve the thermal stability of the copolymer.
[0053] The preparation method of the present invention will be described in detail below:
[0054] S1: A mixture of 4,4'-difluorobenzophenone and a dihydroxy compound undergoes a polycondensation reaction;
[0055] S2: Add a capping agent to the reaction system, wherein the capping agent is selected from at least one of phenol, 4-tert-butylphenol or 4,4'-difluorobenzophenone;
[0056] The mixture of dihydroxy compounds includes 1,4-dihydroxynaphthalene or 1,5-dihydroxynaphthalene, and at least one of 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl, 1,3-dihydroxybenzene or 1,2-dihydroxybenzene;
[0057] The molar content of the 1,4-dihydroxynaphthalene or 1,5-dihydroxynaphthalene is 10% to 50% of the total molar amount of the dihydroxy compound mixture.
[0058] The polycondensation reaction is carried out under alkaline conditions, which are achieved by adding an alkaline compound selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide. Specific reaction temperatures, pressures, and other conditions are common knowledge to those skilled in the art and will not be elaborated upon here.
[0059] Furthermore, in step S2, the molar ratio of the mixture of 4,4'-difluorobenzophenone and the dihydroxy compound is 1.005:1 to 1.05:1.
[0060] Furthermore, the mixture of dihydroxy compounds includes at least one of 1,4-naphthol, 1,5-naphthol, 1,6-naphthol, 2,3-naphthol, or 2,7-naphthol, and 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl, 1,3-dihydroxybenzene, or 1,2-dihydroxybenzene.
[0061] Furthermore, the present invention also provides tubes or sleeves formed from compositions comprising or composed of copolymers according to the first aspect of the present invention.
[0062] The present invention also provides a method for forming tubes or sleeves by extruding a composition comprising or consisting of a copolymer according to the present invention.
[0063] This invention lowers the melting point of the material by introducing a naphthol structure while maintaining good high-temperature resistance; it reduces production costs by using a low-cost 1,4-naphthol structure raw material route; the melting point and melt viscosity of the material can be flexibly adjusted by controlling the proportion of different structural units; it improves the processing performance of the material, making it more suitable for industrial applications such as carbon fiber impregnation; the material has good thermal stability and mechanical properties, and can be widely used in aerospace, new energy vehicles, wind power and other fields.
[0064] The copolymers were prepared as described in Examples 1 to 7. During the preparation process, the copolymerization progress was monitored by measuring the torque applied to the reaction stirrer. The torque increased with increasing copolymer molecular weight (degree of polymerization). The reaction was terminated when the target torque was reached, or after 50–60 minutes (if the target torque was not reached at this time), as described below. As the polymer molecular weight increases, the viscosity of the solution in the reaction mixture also increases, resulting in an increase in the torque of the reaction stirrer. Under similar reaction conditions for the preparation of PEEK, the target torque was expected to be approximately 0.15 to 0.45 kNsm. -2 The MV of PEEK. Example 1 provides a detailed description of the procedures and tests performed on the copolymers of the examples.
[0065] Example 1
[0066] Preparation of PEEK-PEDEK-PENEK copolymers including 1,4-dihydroxynaphthalene copolymer monomer (providing RPENEK) - using lithium salt and copolymer end-capping to terminate the reaction.
[0067] In this embodiment, the monomers for copolymerizing 1,4-dihydroxybenzene and 4,4′-dihydroxybiphenyl are mixed with 1,4-dihydroxynaphthalene to provide a PEEK-PEDEK-PENEK copolymer with RPEEK:RPEDEK:RPENEK = 88 / 10 / 2.
[0068] Once the desired torque / MV is reached, the reaction is stopped by adding lithium sulfate, followed by using 4,4'-difluorobenzophenone to provide a copolymer with the following fluorobenzophenone terminal units:
[0069] The details are as follows.
[0070] In a 0.5-liter flanged bottle equipped with a frosted glass lid, a stirrer / stirrer guide, and nitrogen inlet and outlet, 4,4'-difluorobenzophenone (110.19 g, 0.505 mol), 1,4-dihydroxybenzene (48.4 g, 0.44 mol), 4,4'-dihydroxybiphenyl (9.3 g, 0.05 mol), 1,4-dihydroxynaphthalene (1.6 g, 0.02 mol), and diphenyl sulfone (303.00 g) were added, and the mixture was purged with nitrogen for 1 hour. The contents were then heated to 150°C under a nitrogen atmosphere to form an almost colorless solution. While maintaining the nitrogen atmosphere, dry sodium carbonate (54.58 g, 0.515 mol) and potassium carbonate (0.35 g, 0.0025 mol), both sieved through a 500-micron mesh, were added. The temperature was increased to 270°C at a rate of 1°C / min and maintained until the desired torque was achieved. Lithium sulfate (0.96 g, 0.00875 mol) and 4,4'-difluorobenzophenone (1.36 g, 0.00625 mol) were added. The reaction mixture was then maintained at 270°C for another 30 minutes. The reaction mixture was then poured into a foil tray for cooling, milled, and washed with 2 liters of acetone at 40–50°C, followed by washing with warm water until the conductivity of the wastewater was <2 μS. The resulting polymer powder was dried in an air oven at 120°C for 12 hours.
[0071] Example 2 (End-capped)
[0072] In a 0.5-liter flanged bottle equipped with a frosted glass lid, a stirrer / stirrer guide, and nitrogen inlet and outlet, 4,4'-difluorobenzophenone (110.19 g, 0.505 mol), 1,4-dihydroxybenzene (35.75 g, 0.325 mol), 4,4'-dihydroxybiphenyl (9.3 g, 0.05 mol), 1,4-dihydroxynaphthalene (20 g, 0.125 mol), and diphenyl sulfone (303.00 g) were added, and the mixture was purged with nitrogen for 1 hour. The contents were then heated to 150°C under a nitrogen atmosphere to form an almost colorless solution. While maintaining the nitrogen atmosphere, dry sodium carbonate (54.58 g, 0.515 mol) and potassium carbonate (0.35 g, 0.0025 mol), both sieved through a 500-micron mesh, were added. The temperature was increased to 270°C at a rate of 1°C / min and maintained until the desired torque was achieved. Lithium sulfate (0.96 g, 0.00875 mol) and 4,4'-difluorobenzophenone (1.36 g, 0.00625 mol) were added. The reaction mixture was then maintained at 270°C for another 30 minutes. The reaction mixture was then poured into a foil tray for cooling, milled, and washed with 2 liters of acetone at 40–50°C, followed by washing with warm water until the conductivity of the wastewater was <2 μS. The resulting polymer powder was dried in an air oven at 120°C for 12 hours.
[0073] Example 3
[0074] Preparation of 0.5 mol polyether ether ketone (PEEK-PEDEK-PENEK) copolymer (RPEEK:RPEDEK:RPENEK = 65:10:25).
[0075] 4,4'-Difluorobenzophenone (111.56 g, 0.511 mol), 1,4-dihydroxybenzene (35.75 g, 0.325 mol), 4,4'-dihydroxybiphenyl (9.3 g, 0.050 mol), 1,4-dihydroxynaphthalene (20 g, 0.125 mol), and diphenyl sulfone (314.94 g) were added to a 0.5-liter flanged bottle equipped with a frosted glass lid, a stirrer / stirrer guide, and a nitrogen inlet and outlet. The bottle was then purged with nitrogen for 1 hour. The contents were then heated to 150°C under a nitrogen atmosphere to form an almost colorless solution. While maintaining the nitrogen atmosphere, dry sodium carbonate (53.42 g, 0.504 mol) and potassium carbonate (2.764 g, 0.02 mol), both sieved through a 500-micron mesh, were added. The temperature was increased to 180°C at a rate of 1°C / min and held for 100 minutes. The temperature was then increased to 200°C at a rate of 0.5°C / min; subsequently, it was increased to 305°C at a rate of 1°C / min and held for approximately 60 minutes, or until the desired degree of polymerization was achieved as indicated by the increase in torque of the stirrer. The reaction mixture was then poured into a foil tray for cooling, milling, and washed with 2 liters of acetone at 40–50°C, followed by washing with warm water until the conductivity of the wastewater was <2 μS. The resulting polymer powder was dried in an air oven at 120°C for 12 hours.
[0076] Example 4
[0077] Preparation of a PEEK-mPEEK mixed oPEEK-RPEDEK-PENEK copolymer comprising a monomer for copolymerization of 1,3-dihydroxybenzene (providing RmPEEK repeating units) and a monomer for copolymerization of 1,2-dihydroxybenzene (providing RoPEEK repeating units).
[0078] In this embodiment, the monomers used for copolymerizing 1,3-dihydroxybenzene or 1,2-dihydroxybenzene are used in combination with 1,4-dihydroxybenzene to provide a PEEK-mPEEK mixed oPEEK-RPEDEK-PENEK copolymer of RPEEK:RmPEEK mixed RoPEEK:RPEDEK:RPENEK = 55 / 5+5 / 10 / 25.
[0079] In a 0.5-liter flanged bottle equipped with a frosted glass lid, a stirrer / stirrer guide, and nitrogen inlet and outlet, 4,4'-difluorobenzophenone (111.56 g, 0.511 mol), 1,4-dihydroxybenzene (30.25 g, 0.275 mol), 1,3-dihydroxybenzene (2.75 g, 0.025 mol), 1,2-dihydroxybenzene (2.75 g, 0.025 mol), 4,4'-dihydroxybiphenyl (9.3 g, 0.050 mol), 1,4-dihydroxynaphthalene (20 g, 0.125 mol), and diphenyl sulfone (314.94 g) were added and the mixture was purged with nitrogen for 1 hour. The contents were then heated to 150°C under a nitrogen atmosphere to form an almost colorless solution. While maintaining a nitrogen atmosphere, dry sodium carbonate (53.42 g, 0.504 mol) and potassium carbonate (2.764 g, 0.02 mol), both sieved through a 500-micron mesh, were added. The temperature was increased to 180°C at 1°C / min and held for 100 minutes. The temperature was then increased to 200°C at 0.5°C / min; subsequently, it was increased to 305°C at 1°C / min and held for approximately 60 minutes, or until the desired degree of polymerization was achieved as indicated by the torque increase of the stirrer. The reaction mixture was then poured into a foil tray for cooling, milling, and washed with 2 liters of acetone at 40–50°C, followed by washing with warm water until the conductivity of the wastewater was <2 μS. The resulting polymer powder was dried in an air oven at 120°C for 12 hours.
[0080] Example 5
[0081] Preparation of 0.5 mol polyether ether ketone (PEEK-PEDEK-PENEK) copolymer (RPEEK:RPEDEK:RPENEK = 40:20:40).
[0082] 4,4'-Difluorobenzophenone (111.56 g, 0.511 mol), 1,4-dihydroxybenzene (22 g, 0.2 mol), 4,4'-dihydroxybiphenyl (18.6 g, 0.1 mol), 1,4-dihydroxynaphthalene (32 g, 0.2 mol), and diphenyl sulfone (314.94 g) were added to a 0.5-liter flanged bottle equipped with a frosted glass lid, a stirrer / stirrer guide, and a nitrogen inlet and outlet. The bottle was then purged with nitrogen for 1 hour. The contents were then heated to 150°C under a nitrogen atmosphere to form an almost colorless solution. While maintaining the nitrogen atmosphere, dry sodium carbonate (53.42 g, 0.504 mol) and potassium carbonate (2.764 g, 0.02 mol), both sieved through a 500-micron mesh, were added. The temperature was increased to 180°C at a rate of 1°C / min and maintained for 100 minutes. The temperature was increased to 200°C at a rate of 0.5°C / min; then increased to 305°C at a rate of 1°C / min and held for approximately 60 minutes, or until the desired degree of polymerization was achieved as indicated by the increase in torque of the stirrer. The reaction mixture was then poured into a foil tray for cooling, milling, and washed with 2 liters of acetone at 40–50°C, followed by washing with warm water until the conductivity of the wastewater was <2 μS. The resulting polymer powder was dried in an air oven at 120°C for 12 hours.
[0083] Example 6
[0084] Repeat the steps described in Example 5, keeping the total ratio of 1,4-dihydroxybenzene to 4,4'-dihydroxybiphenyl and 1,4-dihydroxynaphthalene constant, to provide a PEEK-PEDEK-PENEK copolymer with a PEEK:PEDEK:PENEK component ratio of 40:20:40.
[0085] As shown in Table 1 below, the polymer material provided in Example 5 has a significantly lower Tm compared to the PEEK-PEDEK-PENEK copolymer, a partially lower Tg compared to the PEEK-PEDEK-PENEK copolymer, and a comparable level of crystallinity.
[0086] The polymer material was prepared according to Example 6, and an additive was added to the polymer material at the end of the reaction to increase the crystallization rate of the polymer material. Ten minutes after the torque increase stopped, 7.59 g of Victrex ST45PF (purchased from Victrex Manufacturing Limited, Victrex Technology Centre, Hillhouse International, Thornton Cleveleys, FY54QD, UK) was added to the polymer material. After stirring for another 10 minutes, the reaction mixture was poured into a foil tray and cooled, ground, and washed according to the procedure in Example 1. Victrex ST45PF is a polyetherketone (PEKEKK) composition; or a commercially available additive—a polyetherketone (PEKEKK) composition—can be purchased.
[0087] To compare the effects of different copolymer compositions on thermal properties, differential scanning calorimetry (DSC) was performed on the copolymers prepared in Examples 1 to 6 to determine the glass transition temperature (Tg), melting temperature (Tm), crystallization temperature (Tc), and crystallinity (X%). The results are summarized in Table 1.
[0088] Table 1 Thermal property data of copolymers in Examples 1-6
[0089] As can be seen from Table 1, the polymer material provided in Example 5 has a significantly lower Tm compared to the PEEK-PEDEK-PENEK copolymer, a partially lower Tg compared to the PEEK-PEDEK-PENEK copolymer, and a comparable level of crystallinity.
[0090] The additive Victrex ST45PF leads to an increased crystallization rate, as shown by the increase in Tc in Example 6. Without being bound by theory, it is assumed that the ST45PF powder particles are nucleation sites, thus improving the crystallization rate of the polymer material through heterogeneous crystallization. The benefit of this increased crystallization rate is that the polymer material can be used in various manufacturing methods, including those requiring rapid crystallization, such as injection molding.
[0091] Example 7
[0092] The procedure described in Examples 1-4 was repeated on a larger scale using a 50L jacketed steel container. Preparation of 25 mol of polyetheretherketone (PEEK-PEDEK-PENEK) copolymer (RPEEK:RPEDEK:RPENEK = 65:10:25).
[0093] Diphenyl sulfone (15.8 kg) was placed in a container and allowed to melt. When the contents were melted and the temperature reached 140 to 150°C, the stirring was set to 20 rpm, and the following materials were added sequentially: 1,4-dihydroxybenzene (1.788 kg, 16.25 mol), 4,4'-dihydroxybiphenyl (0.465 kg, 2.5 mol), 1,4-dihydroxynaphthalene (1.0 kg, 6.25 mol), and 4,4'-difluorobenzophenone (5.578 kg, 25.60 mol). When the temperature of the contents reached 140 to 150°C, a mixture of sodium carbonate (2.671 kg, 25.2 mol) and potassium carbonate (0.138 kg, 1.0 mol), pre-sieved through a 500 μm sieve, was added to the container.
[0094] Increase the stirring speed to 50 rpm, and adjust the temperature of the contents at 0.3℃ / min. - 1. Increase to 200℃, then increase by 1℃ / min. - 1. Increase the temperature to 305°C. Maintain the temperature at 305°C until sufficient viscosity is achieved. The molten mixture is discharged from the reactor over approximately 45 minutes, and the solidified material is ground into a coarse powder (maximum size <2 mm). The powder is transferred to a column pre-permeated with acetone until the leachate no longer precipitates upon the addition of water. The product is then washed with deionized water at 50°C to remove aqueous byproducts. Once the conductivity of the leachate is measured to be <2 μS using a conductivity probe, the remaining material in the column is discharged and dried in an air-circulating oven at 150°C.
[0095] To further evaluate the thermal stability of the copolymers, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed on the copolymers prepared in Examples 1 to 7. In addition to Tg, Tm, and crystallinity, the 5% thermogravimetric temperature (Td5) was also determined to assess the thermal stability of the materials. The test results are summarized in Table 2.
[0096] Table 2. Thermal properties and thermal stability data of copolymers in Examples 1-7
[0097] As can be seen from Table 2, Examples 1-7 modified the RPEEK:PEEK-PEDEK:RPENEK copolymer by reducing the RPEEK molar ratio and increasing the molar ratio of RmPEEK mixed with RoPEEK:RPEDEK:RPENEK respectively; among which Example 4 modified the specific RPEEK:PEEK-PEDEK:RPENEK copolymer by replacing some RPEEK units with RmPEEK mixed with RoPEEK units; based on the Tg of Example 1, the following results were obtained:
[0098] i) Tg partially increases;
[0099] ii) Tg is partially reduced;
[0100] iii) It has little effect on Td5;
[0101] iv) and the crystallinity is partially reduced, but there is still a significant degree of crystallinity.
[0102] In summary, the copolymers provided by this invention comprise repeating units of -ether-phenyl-ether-phenyl-carbonyl-phenyl, -ether-biphenyl-ether-phenyl-carbonyl-phenyl, and ether-naphthyl-phenyl-ether-phenyl-carbonyl-phenyl. By partially replacing the para-RPEEK units with RoPEEK and / or RmPEEK units, the melting temperature is reduced, wherein the ether-phenyl-ether moiety is at the ortho and meta positions rather than the para position. This copolymer exhibits crystallinity and a glass transition temperature similar to that of prior art polymers without partial para-substitution. By partially replacing the para-RPEEK units with biphenyl-RPEDEK units and para-RPENEK units, the crystallinity of the copolymer is significantly improved, and it exhibits a higher glass transition temperature than prior art polymers without partial para-substitution.
[0103] Furthermore, to optimize copolymer performance and expand its application range, the following two aspects of research were conducted: First, copolymer variants with different molecular weights and compositions were obtained by adjusting formulation parameters (such as monomer ratio, solvent dosage, etc.) (Examples 8-9, 11); Second, the processing and mechanical properties of the copolymers were improved by introducing functional additives. Two methods of additive introduction were used: one was to add the additive directly at the termination of the polymerization reaction (Examples 10, 12), and the other was to add the additive during subsequent melt processing using a twin-screw extruder (Examples 13-18). The latter included adding nucleating agents to increase the crystallization rate (Examples 13-14) and adding elastomers to improve impact toughness (Examples 15-18).
[0104] Example 8
[0105] Example 7 was repeated, but with a reduced charge of 5.545 kg of 4,4'-difluorobenzophenone.
[0106] Example 9
[0107] Example 7 was repeated, but 11.013 kg of diphenyl sulfone was used.
[0108] Example 10
[0109] Example 9 was repeated, but at the termination of the polymerization reaction, 0.39 kg of fine ST 45PF powder (PEKEKK) was added to the reaction mixture. The mixture was stirred for another 30 minutes, then discharged, and carried out as described in the previous Example 7.
[0110] Example 11
[0111] Example 9 was repeated, but with a reduced charge of 5.7 kg of 4,4'-difluorobenzophenone.
[0112] Example 12
[0113] Example 10 was repeated, but with a reduced charge of 5.7 kg of 4,4'-difluorobenzophenone.
[0114] To compare the effects of adding additives during the polymerization reaction (Examples 10, 12) versus adding additives during post-processing extrusion, the following examples were conducted. The advantage of this approach is that it allows for more flexible adjustment of the additive content and is applicable to pre-synthesized copolymer substrates.
[0115] Example 13
[0116] 1.93 kg of polyaryletherketone from Example 7 was prepared by adding Victrex ST45PF (PEKEKK) during melt processing.
[0117] In this embodiment, the polymer material was prepared according to Example 7. Additives were then added to the polymer material in a subsequent melt processing step to increase its crystallization rate. 96.5 g of Victrex ST45PF (available from Victrex Manufacturing Limited, Victrex Technology Centre, Hillhouse International, Thornton Cleveleys, FY54QD, UK) was added to 1.83 kg of polymer material and fed into the back feed section of a Coperion ZSK25 twin-screw extruder via a separate weight-reducing feeder at a barrel temperature of 310 to 320°C. The resulting mixture was then extruded into two laces with a diameter of 4 mm, cooled on a conveyor belt, and then granulated into particles with a length of 2.0 to 4.0 mm.
[0118] Example 14
[0119] 1.93 kg of polyaryletherketone from Example 8 was prepared by adding Victrex ST45PF (PEKEKK) during melt processing.
[0120] In this embodiment, the polymer material was prepared according to Example 8. Additives were then added to the polymer material in a subsequent melt processing step to increase its crystallization rate. 96.3 g of Victrex ST45PF (available from Victrex Manufacturing Limited, Victrex Technology Centre, Hillhouse International, Thornton Cleveleys, FY54QD, UK) was added to 1.83 kg of polymer material and fed into the back feed section of a Coperion ZSK25 twin-screw extruder via a separate weight-reducing feeder at a barrel temperature of 310 to 320°C. The resulting mixture was then extruded into two 4 mm diameter strips, cooled on a conveyor belt, and then granulated into particles with a length of 2.0 to 4.0 mm.
[0121] Besides improving the crystallization rate, the impact toughness of copolymers is also an important performance indicator for applications. To this end, elastomer additives are added during the extrusion process to reduce material stiffness and improve impact strength, including thermoplastic copolyester elastomers (TPC-ET) and polyetherimide-siloxane copolymers (PEI-siloxane).
[0122] Example 15
[0123] Hytrel 5555HS (TPC-ET) was added during melt processing to prepare 0.8 kg of polyarylether ketone in Example 7.
[0124] In this embodiment, the polymer material was prepared according to Example 7. Additives were then added to the polymer material in a subsequent melt processing step to reduce its stiffness and improve its impact performance. 80 g of Hytrel 5555HS (available from DuPont, 974 Centre Road, Wilmington, DE 19805, USA) was added to 0.72 kg of the polymer material and fed into the back feed section of a Coperion ZSK25 twin-screw extruder via a separate weight-reducing feeder at a barrel temperature of 290°C. The resulting mixture was then extruded into two 4 mm diameter strips, cooled on a conveyor belt, and then granulated into particles with a length of 2.0 to 4.0 mm.
[0125] Example 16
[0126] Hytrel 5555HS (TPC-ET) was added during melt processing to prepare 0.8 kg of polyarylether ketone in Example 7.
[0127] In this embodiment, the polymer material was prepared according to Example 7. Additives were then added to the polymer material in a subsequent melt processing step to reduce its stiffness and improve its impact performance. 0.16 kg of Hytrel 5555HS (available from DuPont, 974 Centre Road, Wilmington, DE 19805, USA) was added to 0.64 kg of the polymer material and fed into the back feed section of a Coperion ZSK25 twin-screw extruder via a separate weight-reducing feeder at a barrel temperature of 290°C. The resulting mixture was then extruded into two 4 mm diameter strips, cooled on a conveyor belt, and then granulated into particles with a length of 2.0 to 4.0 mm.
[0128] Example 17
[0129] 0.8 kg of polyaryletherketone from Example 7 was prepared by adding Siltem 1500 (PEI-siloxane copolymer) and Ultem 1000 (PEI) during melt processing.
[0130] In this embodiment, the polymer material was prepared according to Example 7. Two additives were then added to the polymer material in a subsequent melt processing step to reduce its stiffness and improve its impact performance. 80 g of Siltem 1500 and 40 g of Ultem 1000 (both available from Sabic, SAUDI BASIC INDUSTRIES CORPORATION (HQ), PO Box 5101, Riyadh 11422, Saudi Arabia) were added to 0.68 kg of the polymer material and fed into the rear feed section of a Coperion ZSK25 twin-screw extruder via separate weight-reducing feeders at a barrel temperature of 290°C. The resulting mixture was then extruded into two 4 mm diameter strips, cooled on a conveyor belt, and then granulated into particles with a length of 2.0 to 4.0 mm.
[0131] Example 18
[0132] 0.8 kg of polyaryletherketone from Example 7 was prepared by adding Siltem 1500 (PEI-siloxane copolymer) and Ultem 1000 (PEI) during melt processing.
[0133] In this embodiment, the polymer material was prepared according to Example 7. Two additives were then added to the polymer material in a subsequent melt processing step to reduce its stiffness and improve its impact performance. 80g of Siltem 1500 and 80g of Ultem 1000 (both available from Sabic, SAUDI BASIC INDUSTRIES CORPORATION (HQ), PO Box 5101, Riyadh 11422, Saudi Arabia) were added to 0.64kg of the polymer material and fed into the rear feed section of a Coperion ZSK25 twin-screw extruder via separate weight-reducing feeders at a barrel temperature of 290°C. The resulting mixture was then extruded into two 4mm diameter strips, cooled on a conveyor belt, and then granulated into particles with a length of 2.0 to 4.0mm.
[0134] Furthermore, to comprehensively evaluate the properties of the prepared copolymers and their modified materials, systematic thermal characterization (differential scanning calorimetry, TGA), rheological property testing (capillary rheometer and rotational rheometer), and mechanical property testing (tensile, bending, and impact) were conducted. These test results not only validated the design objectives of the copolymers but also provided crucial data support for the practical application of the materials.
[0135] Example 19: Thermal Performance Characterization
[0136] Differential scanning calorimetry of the copolymers in Examples 1 to 7.
[0137] Crystallinity can be assessed using several methods, such as density method, IR spectroscopy, X-ray diffraction, or differential scanning calorimetry. In this example, a Mettler Toledo DSC1 Star system with an FRS5 sensor was used to evaluate the crystallinity of the polymers formed in Examples 1 to 7 using the DSC method.
[0138] The glass transition temperature (Tg), melting temperature (Tm), and heat of fusion (Hm) of the polymers in Examples 1 to 7 were determined using the following DSC method.
[0139] The dried samples of each polymer were compressed into amorphous films as follows: 7g of polymer was heated in a mold at 400°C for 2 minutes under a pressure of 50 bar, followed by quenching in cold water, to produce films with dimensions of approximately 120×120mm and a thickness of approximately 0.20mm. Samples of each film (8mg ± 3mg) were scanned by DSC, as shown below:
[0140] Step 1: Perform and record the initial thermal cycling by heating the sample from 50°C to 400°C at a rate of 20°C / min.
[0141] Step 2, hold for 5 minutes.
[0142] Step 3: Cool at 50°C / min to the midpoint between Tg1 and Tm1 recorded in the first cycle (Tg1 is the point of maximum slope obtained during glass transition when heating in Step 1. Tm1 is the temperature at which the endothermic melting in Step 1 reaches its maximum value).
[0143] Step 4, keep for 3 hours.
[0144] Step 5: Cool to 50°C at 50°C / min and hold for 5 minutes.
[0145] Step 6: Reheat from 50°C to 400°C at a rate of 20°C / min, and record the heat absorption values Tg, Tm, and ΔHm of this second heating.
[0146] Based on the DSC trajectory obtained in step 6, the temperature Tg with the maximum endothermic slope during glass transition is obtained. Tm is the temperature at which the melting endothermic temperature reaches its maximum value.
[0147] The heat of fusion (ΔHm) is obtained by connecting two points of endothermic melting relative to the straight baseline above Tg in step 6. The enthalpy of fusion conversion is generated by the endothermic underintegral area as a function of time. The mass-normalized heat of fusion is calculated by dividing the enthalpy by the sample mass (J / g). The crystallinity level (%) is determined by dividing the sample's heat of fusion by 130 J / g. This value of 130 J / g is the heat of fusion for fully crystallized PEEK and is used as a reference value for this measurement.
[0148] The results are listed in Tables 1 and 2 above.
[0149] Thermogravimetric analysis of polyaryletherketones in Examples 1 to 7:
[0150] The thermal stability of a polymer can be measured by evaluating the temperature at which a 5% (wt%) polymer mass loss occurs when the temperature in air is increased at a constant rate from room temperature to 800–1000 °C. Td5 is appropriately measured by thermogravimetric analysis (TGA). The TGA method was used to measure Td5 using a TA instrument TGAQ5000 and a platinum plate balanced in air. The temperature was increased from room temperature to 800–1000 °C at a rate of 50 °C per minute, and the rate was reduced to 1 °C per minute when a 0.1% weight loss of the sample was detected.
[0151] The results are shown in Table 2, where the examples are grouped together with other examples having the same total (RPEEK+RoPEEK+RmPEEK):RPEDEK:RPENEK ratio.
[0152] Differential scanning calorimetry (DSC) was performed on Examples 7, 8, 10, 12, 13 and 14.
[0153] According to ISO 11357, the melting temperature (Tm), crystallization temperature (Tc), glass transition temperature (Tg), and heat of fusion (ΔH) of Examples 7, 8, 10, 12, 13, and 14 were determined using another differential scanning calorimetry (DSC) method. The instrument used was a TA Instruments Q200.
[0154] The heat cycle is as follows:
[0155] First thermal cycle: from 50.0℃ to 320.0℃ at a rate of 20.0℃ / min, with isothermal treatment for 5 minutes.
[0156] First cooling cycle: from 320.0℃ to 50.0℃ at a rate of 20.0℃ / min, with isothermal treatment for 5 minutes.
[0157] Second thermal cycle: from 50.0℃ to 320.0℃ at a rate of 20.0℃ / min, with isothermal treatment for 5 minutes.
[0158] Tm is the peak temperature at which the endothermic reaction during melting reaches its maximum value in the second thermal scan.
[0159] Tc is the peak temperature of the exothermic crystallization obtained from the first cold scan.
[0160] The glass transition temperature (Tg), the onset point, and the midpoint were determined in the second thermal scan.
[0161] The enthalpy of fusion ΔH was determined in the second thermal scan and the area was calculated by plotting a linear baseline from slightly above Tg(174℃) / (157℃) to above the temperature of the last endothermic reaction.
[0162] The normalized heat of fusion is calculated by dividing the enthalpy by the sample mass (J / g). The crystallinity level (%) is determined by dividing the sample's heat of fusion by 130 J / g. This value of 130 J / g is the heat of fusion for fully crystallized PEEK and is used as a reference value for this measurement.
[0163] To evaluate the performance differences between the copolymers of the present invention and commercially available PEEK materials, the copolymers of Examples 7 and 8 were compared with Victrex PEEK 150G and Victrex PEEK 450G, and the results are summarized in Table 3.
[0164] Table 3 shows the material properties from Examples 7 and 8 and the comparative examples from DSC.
[0165] As shown in Table 3, the melt temperature of the copolymer is significantly lower compared to Victrex PEEK 150G and Victrex PEEK 450G. This results in a material that is easier to process at lower temperatures, while opening up the possibility of using additives that are not suitable for PEEK polymers due to the higher processing temperatures required for processing PEEK in combination with the copolymer.
[0166] Examples 10, 12, 13, and 14 are copolymer compositions with added Victrex ST45PF (Victrex ST45PF is polyetherketone ketone PEKEKK). The melt temperature of Victrex ST45PF is approximately 387°C. By adding ST45PF, the present invention enables the production of polymer materials with shortened crystallization times, as shown in Table 4. As a result, the composition crystallizes much faster than the copolymer itself. One advantage of increasing the crystallization rate of the copolymer is that when manufacturing parts from the copolymer, the number of molding cycles can be increased, thereby increasing the number of parts manufactured per minute.
[0167] Table 4 Crystallization behavior of Examples 10, 12, 13 and 14
[0168] Example 20
[0169] Rheological properties are important indicators for evaluating the processing performance of polymers. By measuring the melt viscosity at high shear rates using a capillary rheometer and the viscosity at low shear rates using a rotational rheometer, a comprehensive understanding of the material's flow behavior under different processing conditions can be obtained.
[0170] High Shear Rate Viscosity Measurement: The melt viscosity of the PAEK copolymer was measured using a capillary rheometer equipped with a RH10 capillary rheometer (Malvern Instruments Rosand RH10 capillary rheometer) with a 0.5 mm (capillary diameter) × 8.0 mm (capillary length) tungsten carbide die. Approximately 5 g of copolymer was dried in an air-circulating oven at 150°C for 3 hours. The extruder was equilibrated to 400°C. The dried polymer was loaded into the heating cylinder of the extruder, with the brass end (12 mm long × 9.92 ± 0.01 mm diameter) positioned on top of the polymer. The piston and screw were then manually rotated until the pressure gauge's sealing ring engaged precisely with the piston to help purge any trapped air. The polymer column was allowed to heat and melt for at least 10 minutes. After the preheating phase, the screw was started to rotate, causing the molten polymer to be extruded through the die at the desired shear rate to form thin fibers, while the pressure (P) required to extrude the polymer was recorded.
[0171] The melt viscosity is given by the following formula:
[0172] Melt viscosity = (Pπr) 4) / (8LSA)kNsm - 2
[0173] Where P = pressure / kN m -2 L = Die length / m; S = Stamping speed / ms -1 A = Cross-sectional area of cylinder / m 2 r = mold radius / m.
[0174] The relationship between shear rate and other parameters is expressed by the following formula: Apparent wall shear rate = 4Q / πr 3 Where Q = volumetric flow rate / m 3 s -1 =SA.
[0175] Therefore, by adjusting the stamping speed S, different shearing rates (such as 100, 1000, or 10000 s) can be achieved. -1 The viscosity of molten polymer was measured under the following conditions.
[0176] Figures 1 and 2 illustrate the shear viscosity behavior of Examples 7 and 8 using the method described in Example 20 above. Comparative examples, including Victrex 150G and Victrex 450G (available from Victrex Manufacturing Limited, Victrex Technology Centre, Thornton Cleveleys, UK), are also shown. Comparative examples from other PAEK suppliers are also shown (e.g., KT880 from Solvay Speciality Polymers USA, LLC, 4500 McGinnis Ferry Road, Alpharetta, Georgia, USA, and L4000 from Evonik Industries AG, Rellinghauser Straße 1-11, 45128 Essen, Germany). Examples 7 and 8 illustrate the flow properties between comparative polyetheretherketones.
[0177] Low shear rate viscosity of polymer materials (0.006 s⁻¹) -1 up to 628.319s -1 A rotational rheometer can be used for measurement, using TAInstruments. TMThe Discovery Hybrid Rheometer-2 (DHR-2) is equipped with an Environmental Testing Chamber (ETC), a 25mm stainless steel parallel plate, and a 25mm stainless steel stepped lower ETC plate. 1.6g of the copolymer was dried in an air-circulating oven at 150°C for approximately 3 hours. The extruder was then equilibrated to the test temperature (typically 300-400°C).
[0178] The dried copolymer was loaded into a melt ring encased in the stepped portion of the lower plate. Once the chamber temperature returned to the test temperature, a 3-minute delay was sufficient to melt the copolymer, after which the melt ring was removed. The gap between the two plates was closed at a rate of 200 μm / s until the gap size reached 1075 μm. After a further 2-minute delay, excess polymer material was removed from the gap using a 6 mm trimming tool. Before starting the test, once trimmed, the gap was closed again at a rate of 200 μm / s to 1000 μm.
[0179] Viscosity is derived from the following formula:
[0180] Viscosity (η)=(MKσPa.s) / (ΩKγ)
[0181] Where: M = torque / Nm -1 Kσ = stress constant; Ω = motor angular velocity / rad / s -1 ; γ = strain constant.
[0182] For parallel plates, Kσ = 2 / (πr) 3 Kγ = r / h;
[0183] Where: r = radius of plate / m; h = gap size / m.
[0184] To determine the shear viscosity within the shear rate range, dynamic oscillation experiments were conducted. The torque was kept constant, and the frequency was scanned logarithmically from high to low (typically from 100 Hz to 0.01 Hz), with 5 points taken at each order of magnitude. The complex viscosity was determined as: Complex viscosity (η*) = (G*Pa.s) / ω
[0185] Where: G* = complex modulus / Pa; ω = angular frequency / rad / s -1 .
[0186] Complex viscosity can be converted to viscosity using the Cox-Merz rule, thus obtaining viscosity as a function of shear rate.
[0187] The Cox-Merz rule for linear polymers: η*(ω)=η(γ)@γ=ω.
[0188] Where γ = shear rate / s -1 .
[0189] Figure 2 shows the rheological properties of Examples 7 and 8 compared to Victrex PEEK 150G, Victrex PEEK 450G, and Victrex PEEK 650G (all available from Victrex Manufacturing Limited). The copolymers according to the invention exhibit rheological behavior similar to known PEEKs.
[0190] Example 21
[0191] Besides thermal and rheological properties, mechanical properties are a key indicator for the practical application of materials. To evaluate the suitability of the copolymers and their modified compositions of this invention for structural applications, the tensile properties, flexural properties, and impact strength of the materials were systematically tested according to ISO standards.
[0192] The mechanical properties of the compositions of Examples 7, 8, 11, 15 and 17 were tested at 23°C using Type 1A (ISO 3167) test bars according to ISO standards: tensile properties ISO 527, flexural properties ISO 178 and impact strength ISO 180 / A.
[0193] Mechanical properties of the basic copolymer:
[0194] Tensile properties were first tested on the base copolymers without modifiers (Examples 7, 8, and 11) to evaluate the effect of different formulations on mechanical properties. The test results are summarized in Table 5 and compared with the commercially available PEEK material Victrex PEEK450G.
[0195] Table 5 Tensile mechanical properties of Examples 7, 8 and 11
[0196] As shown in Table 5, this copolymer exhibits good tensile strength properties close to those of Victrex PEEK 450G. Although the tensile modulus and strength are slightly lower than those of commercially available PEEK, they remain at a high level and can meet the requirements of most structural applications.
[0197] To further expand the application range of copolymers, especially in applications requiring high impact toughness, comprehensive mechanical property tests, including tensile, flexural and impact properties, were conducted on copolymer compositions with added elastomers (Examples 15, 17).
[0198] Table 6 shows the mechanical properties of immiscible blends containing the copolymer and elastomer Hytrel 5555HS (TPC-ET). Significantly improved impact resistance was observed by incorporating a small amount of Hytrel 5555HS (TPC-ET) into the composition.
[0199] Table 6 Mechanical properties of immiscible blend compositions
[0200] As shown in Table 6, although the tensile strength and flexural strength decreased slightly after adding Hytrel, the notched impact strength increased from 2.95 kJ / m. 2 Increased to 4.66 kJ / m 2 The increase reached approximately 58%. This indicates that through...
[0201] Adding an appropriate amount of elastomer can significantly improve the toughness of a material while maintaining high stiffness.
[0202] Table 7 shows the mechanical properties of miscible blends containing copolymers and elastomers Siltem and Ultem. Improved impact resistance was also observed by incorporating small amounts of Siltem and Ultem into the composition.
[0203] Table 7 Mechanical properties of miscible blend compositions
[0204] As shown in Table 7, after adding Siltem and Ultem, the notched impact strength increased from 2.9 kJ / m. 2 Significantly increased to 5.7 kJ / m 2 The improvement is close to 100%. This modification method is more effective in improving toughness, providing an effective solution for applications requiring high impact performance.
[0205] The test results above show that the polyaryletherketone copolymer provided by the present invention achieves performance optimization by rationally designing the ratio of Formula I repeating units to Formula II repeating units, and by introducing a specific proportion of 1,4-naphthodiol or 1,5-naphthodiol structural units into the Formula I repeating units.
[0206] In summary, the polyaryletherketone copolymer provided by this invention comprises repeating units of Formula I, repeating units of Formula II, and terminal units, wherein the molar ratio of repeating units of Formula I to repeating units of Formula II is 55:45 to 95:5. By introducing 1,4-naphthol or 1,5-naphthol structural units and optimizing the proportions of each component, this copolymer achieves a reduction in melting point and control of melt viscosity while maintaining good high-temperature resistance.
[0207] This not only reduces production costs but also improves the processing performance of the material. The copolymer exhibits excellent thermal stability and mechanical properties, making it particularly suitable for industrial applications such as carbon fiber impregnation. It can be widely applied to lightweight applications in aerospace, new energy vehicles, wind power, and other fields.
[0208] Obviously, those skilled in the art can make various modifications and variations to this invention without departing from its spirit and scope. Therefore, if these modifications and variations fall within the scope of the claims of this invention and their equivalents, this invention also intends to include these modifications and variations.
Claims
1. A polyaryletherketone copolymer, characterized in that, include: The formula I repeating unit, the formula II repeating unit, and the terminal unit, wherein the molar ratio of the formula I repeating unit to the formula II repeating unit is 55:45 to 95:5; The repeating unit of Equation II is: The repeating unit of formula I includes:
2. The polyaryletherketone copolymer according to claim 1, characterized in that, The Formula I repeating unit comprises 50 to 90 mol% of Formula III repeating units and 10 to 50 mol% of Formula IV repeating units and Formula V independent units, wherein: The repeating unit of Equation III is: The IV repeating unit is: The independent unit of formula V is an RnPEEK structural unit containing a naphthodiol structure, wherein the naphthodiol is selected from at least one of 1,4-naphthodiol, 1,5-naphthodiol, 1,6-naphthodiol, 2,3-naphthodiol and 2,7-naphthodiol.
3. The polyaryletherketone copolymer according to claim 2, characterized in that, The Formula I repeating unit comprises 65 to 90 mol% of Formula III repeating units and 10 to 35 mol% of Formula IV repeating units, Formula V independent units, or mixtures thereof.
4. The polyaryletherketone copolymer according to claim 3, characterized in that, The repeating unit of Formula I includes 80 to 90 mol% of the repeating unit of Formula III and 10 to 20 mol% of the repeating unit of Formula IV, the independent unit of Formula V, or a mixture thereof.
5. The polyaryletherketone copolymer according to claim 1, characterized in that, The Formula I repeating unit comprises 10 to 50 mol% of Formula III repeating units and 50 to 90 mol% of Formula V independent units, wherein the Formula III repeating unit is: The independent unit of formula V is an RnPEEK structural unit containing a naphthodiol structure, wherein the naphthodiol is selected from at least one of 1,4-naphthodiol, 1,5-naphthodiol, 1,6-naphthodiol, 2,3-naphthodiol and 2,7-naphthodiol.
6. The polyaryletherketone copolymer according to claim 1, characterized in that, The molar ratio of the repeating unit of Formula I to the repeating unit of Formula II is 90:10 to 80:
20.
7. The polyaryletherketone copolymer according to claim 1, characterized in that, The terminal groups of the copolymer are -OH groups or -F groups.
8. The polyaryletherketone copolymer according to claim 1, characterized in that, The terminal groups of the copolymer include 9. A method for preparing the polyaryletherketone copolymer as described in any one of claims 1-8, characterized in that, include: A mixture of 4,4'-difluorobenzophenone and a dihydroxy compound was subjected to a polycondensation reaction. An end-capping agent is added to the reaction system, wherein the end-capping agent is selected from at least one of phenol, 4-tert-butylphenol or 4,4'-difluorobenzophenone; The mixture of dihydroxy compounds includes 1,4-dihydroxynaphthalene or 1,5-dihydroxynaphthalene, and at least one of 1,4-dihydroxybenzene, 4,4'-dihydroxybiphenyl, 1,3-dihydroxybenzene or 1,2-dihydroxybenzene; The molar content of the 1,4-dihydroxynaphthalene or 1,5-dihydroxynaphthalene is 10% to 50% of the total molar amount of the dihydroxy compound mixture.
10. The method according to claim 9, characterized in that, The polycondensation reaction is carried out under alkaline conditions, which are achieved by adding an alkaline compound selected from at least one of potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide.
11. The method according to claim 9, characterized in that, The molar ratio of the mixture of 4,4'-difluorobenzophenone and the dihydroxy compound is from 1.005:1 to 1.05:1.