Polyether ether ketone and its manufacturing method

Abstract

The present invention discloses polyetheretherketone and a method for producing the same. The method of the present invention includes the steps of: introducing argon gas into a vessel containing a bisphenol compound to obtain a complex of the bisphenol compound; and mixing a fluoroketone, an alkali metal carbonate, a complex of the bisphenol compound, and a solvent, and performing a temperature programming process on the mixture to produce polyetheretherketone. Thus, before producing polyetheretherketone, the bisphenol compound is protected with argon gas to prevent the bisphenol compound from being oxidized to quinones during the reaction with the fluoroketone and the alkali metal carbonate, and the color value L * The resulting solid polyetheretherketone has a higher viscosity and is whiter in color.

Description

[Technical Field]

[0001] The present invention relates to the field of polymeric materials, and in particular to polyetheretherketones and methods for their production. [Background technology]

[0002] Poly(aryl ether ketone) polymers are new semi-crystalline aromatic thermoplastic engineering plastics developed in the late 1970s. They are linear aromatic polymeric materials that possess high temperature resistance, chemical corrosion resistance, high strength, high modulus of elasticity, high fracture toughness, and excellent dimensional stability. A typical example of poly(aryl ether ketone) polymers is polyether ether ketone, which has a glass transition temperature (Tg) of 143°C, a melting point of 334°C, and a maximum attainable crystallinity of 48%, typically between 20% and 30%. The density in the amorphous state is 1.265 g / cm. 3 and the density at maximum crystallinity is 1.32 g / cm 3 Due to its crystalline form, it has excellent heat resistance and mechanical properties, with a continuous use temperature of 260°C and an instantaneous use temperature of 300°C, and does not decompose in a short time at 400°C. Due to its excellent comprehensive properties, polyether ether ketone is widely used in many fields. The currently commercially available method for synthesizing polyether ether ketone is to use diphenyl sulfone as a solvent and carry out a nucleophilic copolymerization reaction between 4,4'-difluorobenzophenone and 1,4-benzenediol in the presence of carbonate. Polyether ether ketone produced in this way is yellow in color and is widely used, mainly in parts and other fields in various industries.

[0003] However, since whiter polyetheretherketones are required in certain fields, there is a need to further improve the current polyetheretherketones and their manufacturing methods. Summary of the Invention [Problem to be solved by the invention]

[0004] The technical problem that the present invention aims to solve is the chromaticity value L * The question is how to produce polyetheretherketone with higher viscosity and whiter color. [Means for solving the problem]

[0005] Therefore, one object of the present invention is to provide a method for producing polyether ether ketone. The method includes the steps of introducing argon gas into a vessel containing a bisphenol compound to obtain a complex of the bisphenol compound, and mixing a fluoroketone, an alkali metal carbonate, the complex of the bisphenol compound, and a solvent, and subjecting the mixture to a temperature-programmed process to produce polyether ether ketone. Prior to producing polyether ether ketone, the bisphenol compound is protected with argon gas to prevent it from being oxidized to quinones during the reaction with the fluoroketone and the alkali metal carbonate, and the color value L * A solid polyether ether ketone with a higher viscosity and a whiter color is obtained.

[0006] In an embodiment of the present invention, the complex contains an Ar atom, and the formation of the complex includes the steps of introducing argon gas at a flow rate of 20 to 100 ml / min into a vessel containing a bisphenol compound and heating to melt the bisphenol compound, and increasing the flow rate of the argon gas to 150 to 250 ml / min and heating the bisphenol compound to a first predetermined temperature and maintaining the temperature to obtain a complex of the bisphenol compound. This allows the bisphenol compound to be protected with argon gas before the polyetheretherketone is produced, preventing it from being oxidized to quinones during the reaction with the fluoroketone and the alkali metal carbonate, and achieving a chromaticity value L * A solid polyether ether ketone with a higher viscosity and a whiter color is obtained.

[0007] In the present embodiment, after the bisphenol compound is melted, argon gas is introduced under stirring conditions, and the stirring speed is 70 to 100 rpm, which allows the bisphenol compound and argon gas to come into sufficient contact with each other and the reaction to proceed sufficiently.

[0008] In the embodiment of the present invention, the purity of the argon gas is 80% to 100%, which can improve the yield of the complex of the bisphenol compound.

[0009] In an embodiment of the present invention, the first predetermined temperature is 178° C. to 248° C. This allows the bisphenol compound and argon gas to react sufficiently.

[0010] In an embodiment of the present invention, the temperature-rising programming process includes the steps of: heating a mixture of a fluoroketone, an alkali metal carbonate, a complex of a bisphenol compound, and a solvent to a second predetermined temperature to obtain a first solution; heating the first solution to a third predetermined temperature and maintaining the temperature to obtain a second solution; and heating the second solution to a fourth predetermined temperature and maintaining the temperature to obtain a third solution, wherein the second predetermined temperature is 190°C to 210°C, the third predetermined temperature is 270°C to 290°C, and the fourth predetermined temperature is 300°C to 320°C, thereby allowing the reaction to proceed sufficiently.

[0011] In an embodiment of the present invention, the holding time at the second predetermined temperature is 60 to 70 minutes, the holding time at the third predetermined temperature is 50 to 60 minutes, and the holding time at the fourth predetermined temperature is 110 to 130 minutes.

[0012] In an embodiment of the present invention, the temperature programming process is carried out under the protection of an inert gas and further comprises heating the mixture until the mixture melts before heating the mixture to a second predetermined temperature, which allows the reaction to proceed sufficiently.

[0013] In an embodiment of the present invention, the inert gas is argon gas.

[0014] In an embodiment of the present invention, the bisphenol compound includes at least one of hydroquinone and biphenol, and the purity of the hydroquinone is 90% to 103%, which can reduce the occurrence of side reactions.

[0015] In the examples of the present invention, the purity of hydroquinone is 98% to 102%, which can reduce the occurrence of side reactions.

[0016] In an embodiment of the present invention, the fluoroketone includes at least one of 4,4'-difluorobenzophenone, 3,4'-difluorobenzophenone, and 2,4'-difluorobenzophenone, the alkali metal carbonate includes one or two of sodium carbonate, potassium carbonate, strontium carbonate, and cesium carbonate, the solvent includes at least one of sulfolane, diphenyl sulfone, dimethyl sulfoxide, and methylpyrrolidone, and the molar ratio of the bisphenol compound, the fluoroketone, and the alkali metal carbonate is (1-1.2):1:(1-1.1), which allows the reaction to proceed sufficiently.

[0017] In an embodiment of the present invention, the method further includes a step of subjecting the mixed solution containing polyether ether ketone to a separation and purification treatment to obtain solid polyether ether ketone, thereby removing other products produced in the reaction and improving the purity of the polyether ether ketone.

[0018] In the examples of the present invention, the color value (L * ) is (81.15~88.26). This gives a white polyether ether ketone.

[0019] In the examples of the present invention, the color value (L * The range of the product of the viscosity (L*) and the tensile strength (Rm) is 9975 ≧ Rm*L* ≧ 5100. This improves the properties of polyetheretherketone.

[0020] Another aspect of the present invention provides a solid polyetheretherketone. The solid polyetheretherketone is produced by the above-described method, and therefore has all the characteristics and advantages of the polyetheretherketone produced by the above-described method, and further description thereof will be omitted here. Generally, the color value (L * ) and white color. [Brief explanation of the drawings]

[0021] The above and / or additional aspects and advantages of the present invention will become more apparent and easier to understand by reading the following detailed description of the preferred embodiments with reference to the following drawings.

[0022] [Figure 1] 1 is a flowchart of a method for producing polyether ether ketone according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0023] Examples of the present invention are described in detail below. The examples described below are illustrative and are intended to explain the present invention only, and should not be understood as limiting the present invention. Unless specific techniques or conditions are specified in the examples, the techniques and conditions described in the literature in this field or the product specifications shall be followed. Unless the manufacturer is specified, the reagents or equipment used are all ordinary products that are commercially available.

[0024] One aspect of the present invention provides a method for producing polyetheretherketone, comprising the steps of introducing argon gas into a vessel containing a bisphenol compound to obtain a complex of the bisphenol compound, and mixing a fluoroketone, an alkali metal carbonate, the complex of the bisphenol compound, and a solvent, and subjecting the mixture to a temperature-programmed process to produce polyetheretherketone. Prior to producing polyetheretherketone, the bisphenol compound is protected with argon gas to prevent oxidation during the reaction with the fluoroketone and the alkali metal carbonate, resulting in a color value L * The resulting polyether ether ketone is a white solid with high molecular weight.

[0025] For ease of understanding, the principle by which the present method can achieve the above advantageous effects will be briefly explained below.

[0026] As described above, the currently available commercially available method for synthesizing polyether ether ketone involves the nucleophilic copolymerization of 4,4'-difluorobenzophenone and 1,4-benzenediol in the presence of sodium carbonate using diphenyl sulfone as a solvent. Polyether ether ketones produced by this method are yellow in color and are widely used, primarily in various industrial components and other fields. However, certain fields require polyether ether ketones with a whiter color, but no such products are available on the market, and the needs of these fields cannot be met. The present inventors have discovered that the yellow color of polyether ether ketones produced by the current method is due to the oxidation of hydroquinone to quinones during the nucleophilic substitution reaction, which causes the quinones to assume a certain color. In the method according to the present invention, before hydroquinone reacts with 4,4'-difluorobenzophenone and sodium carbonate, hydroquinone is first protected with argon gas to form a hydroquinone complex containing an Ar atom. This prevents hydroquinone from being oxidized to 1,4-benzoquinone in the subsequent nucleophilic substitution reaction, and the hydroquinone complex can directly react with sodium carbonate to form sodium phenolate, thereby carrying out nucleophilic substitution. As a result, the polyether ether ketone produced by this method has a white color.

[0027] Each step of the method will be described in detail below based on an embodiment of the present invention: As shown in Figure 1, the method may include steps S100, S200 and S300.

[0028] Step S100: Argon gas is introduced into a container containing a bisphenol compound.

[0029] In this step, argon gas is introduced into a container containing the bisphenol compound at a flow rate of 20 to 100 ml / min, and the bisphenol compound is melted by heating.

[0030] In some embodiments of the present invention, the flow rate of the argon gas is not particularly limited and can be freely selected by those skilled in the art as needed, and may be, for example, 30, 50, or 80 ml / min. In some embodiments of the present invention, in this step, after the bisphenol compound is heated to melt, the flow rate of the argon gas may be increased, and the bisphenol compound may be heated to and maintained at a first predetermined temperature to obtain a complex of the bisphenol compound containing an Ar atom. In some embodiments of the present invention, the flow rate of the argon gas is not particularly limited and can be freely selected by those skilled in the art as needed to obtain a complex of the bisphenol compound, and may be, for example, 200 ml / min.

[0031] The present inventors discovered that the above treatment allows the bisphenol compound to form a complex with the bisphenol compound. Specifically, the phenolic hydroxyl group in the bisphenol compound can form a weak chemical bond with the Ar atom. The bond between the phenolic hydroxyl group and the Ar atom in this complex is weak, and the complex cannot stably exist for long periods at room temperature. As a result, the complex can continue to form a phenate with the alkali metal carbonate in the subsequent process, and therefore does not affect the subsequent production of polyether ether ketone. However, the Ar atom in the complex formed in this step has a certain protective effect on the phenolic hydroxyl group, preventing the bisphenol compound from being oxidized to a quinone compound before forming the phenate.

[0032] In an embodiment of the present invention, the bisphenol compound includes at least one of hydroquinone and biphenol, and the purity of the hydroquinone is 90% to 103%, preferably 98% to 102%, thereby reducing the occurrence of side reactions.

[0033] In one embodiment of the present invention, the purity of the argon gas is 80% to 100%, preferably 99.0% to 99.9%, and most preferably 99.999%, thereby improving the yield of the complex of the bisphenol compound.

[0034] In one embodiment of the present invention, after the bisphenol compound has melted, argon gas may be continuously introduced under stirring conditions to ensure that the bisphenol compound sufficiently forms a complex. In this step, the rotation speed during stirring may be 70 to 100 rpm, specifically 80 rpm. In this case, the flow rate of the argon gas may be increased, for example, to 150 to 250 ml / min, specifically to approximately 200 ml / min. This allows the bisphenol compound and the argon gas to come into sufficient contact with each other, thereby allowing the reaction to proceed sufficiently.

[0035] In one embodiment of the present invention, the weight of the product after the reaction in this step is greater than the weight of the input raw materials before the reaction, and during the experimental process, before the complex is completely formed, the flow rate of argon gas at the exhaust port of the container is lower than the flow rate of argon gas at the inlet port. This indicates that the argon gas introduced into the container is involved in the reaction, and that what is obtained in this step is not a pure molten bisphenol compound. In a specific embodiment of the present invention, what is obtained in this step is a hydroquinone complex containing an Ar atom.

[0036] The inventors have found that the flow rate and time of argon gas introduction during this step can be adjusted depending on the complex formation status. Specifically, because the reaction between argon gas and the bisphenol compound is concentrated at the interface, adjusting the flow rate of argon gas introduced during this step depending on the volume of the container and the area of ​​the interface ensures that there is enough argon gas inside the container to react with the bisphenol compound at the interface in a timely manner. After the bisphenol compound has melted, the flow rate of argon gas can be increased under stirring conditions to promote faster reaction. When the argon gas flow rates at the container inlet and outlet are detected to be the same, the reaction can be determined to be complete. For example, the holding time at the first predetermined temperature is 1 hour.

[0037] In one embodiment of the present invention, the first predetermined temperature is 178°C to 248°C. Specifically, it may be 188°C, 198°C, 208°C, 218°C, 228°C, 238°C, etc. This allows the bisphenol compound and argon gas to react sufficiently. The heating rate of the bisphenol compound is not particularly limited, and can be selected as needed by a person skilled in the art as long as it satisfies the experimental requirements.

[0038] Step S200: Mix a fluoroketone, an alkali metal carbonate, the complex of the bisphenol compound, and a solvent.

[0039] In this step, a fluoroketone, an alkali metal carbonate, a complex of a bisphenol compound, and a solvent are mixed, and the mixture is subjected to a temperature programming process.

[0040] In the embodiments of the present invention, the type of fluoroketone is not particularly limited and may include, for example, at least one of 4,4'-difluorobenzophenone, 3,4'-difluorobenzophenone, and 2,4'-difluorobenzophenone. Those skilled in the art can select the fluoroketone as needed as long as it satisfies the experimental conditions. This can further improve the properties of the polyether ether ketone obtained by this method.

[0041] In one embodiment of the present invention, the alkali metal carbonate comprises one or two of sodium carbonate, potassium carbonate, strontium carbonate, and cesium carbonate, which can further improve the properties of the polyetheretherketone produced by this method.

[0042] In the embodiments of the present invention, the specific type of solvent is not particularly limited and may include, for example, at least one of sulfolane, diphenyl sulfone, dimethyl sulfoxide, and methylpyrrolidone. Those skilled in the art can select the solvent as needed as long as it satisfies the experimental conditions. Specifically, the use of the high-boiling inert protic solvent can further improve the properties of the polyether ether ketone obtained by this method.

[0043] In one embodiment of the present invention, the molar ratio of the complex of the bisphenol compound, the fluoroketone, and the alkali metal carbonate is (1-1.2):1:(1-1.1), specifically (1-1.2):1:1.1, and more specifically 1:1:1.1.

[0044] The present inventors have found that when the alkali metal carbonate satisfies the above molar ratio, a polyether ether ketone having a small molecular weight and excellent mechanical properties can be obtained, and that the amount of alkali metal carbonate is not excessive, which is advantageous for subsequent separation and purification of the product.

[0045] In an embodiment of the present invention, the temperature-rising programming process includes the steps of: heating a mixture of a fluoroketone, an alkali metal carbonate, a complex of a bisphenol compound, and a solvent to a second predetermined temperature to obtain a first solution; heating the first solution to a third predetermined temperature and maintaining the temperature to obtain a second solution; and heating the second solution to a fourth predetermined temperature and maintaining the temperature to obtain a third solution, wherein the second predetermined temperature is 190°C to 210°C, and the reaction is carried out for 60 to 70 minutes while maintaining the second predetermined temperature; The third predetermined temperature is 270°C to 290°C, and the reaction is carried out for 50 to 60 minutes while maintaining the third predetermined temperature; the fourth predetermined temperature is 300°C to 320°C, and the reaction is carried out for 110 to 130 minutes while maintaining the fourth predetermined temperature; specifically, the second predetermined temperature is 200°C, and the reaction is carried out for 60 minutes while maintaining the second predetermined temperature; the third predetermined temperature is 280°C, and the reaction is carried out for 60 minutes while maintaining the third predetermined temperature; and the fourth predetermined temperature is 305°C, and the reaction is carried out for 120 minutes while maintaining the fourth predetermined temperature. In this way, heating by temperature rise programming can avoid local overheating during the reaction process, improve the uniformity of the reaction, and improve the properties of polyether ether ketone. The temperature increase rates when the mixture is heated to the second predetermined temperature, heated from the second predetermined temperature to the third predetermined temperature, and heated from the third predetermined temperature to the fourth predetermined temperature are not particularly limited, and can be selected as needed by a person skilled in the art as long as the requirements are met.

[0046] In an embodiment of the present invention, the temperature programming process is carried out under the protection of an inert gas, and further includes a step of heating the mixture until the mixture melts before heating the mixture to a second predetermined temperature, which allows the reaction to proceed sufficiently. To further prevent hydroquinone from being oxidized, the inert gas is preferably argon gas.

[0047] In an embodiment of the present invention, the temperature ramping program process is performed under stirring conditions, for example, the rotation speed during stirring may be 60 rpm.

[0048] Step S300: Separation and purification process

[0049] In this step, the third solution is placed in cold distilled water to obtain a white lumpy solid.

[0050] In one embodiment of the present invention, to obtain solid polyetheretherketone, the obtained white lumpy solid needs to be further subjected to separation and purification treatment, which can remove other products produced in the reaction and improve the purity of the polyetheretherketone.

[0051] In one embodiment of the present invention, in this step, the white lumpy solid is crushed into powder, and then washed with ethanol 5-6 times to remove the solvent diphenyl sulfone, and then washed with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, thereby obtaining a white polyether ether ketone powder.

[0052] In one embodiment of the present invention, the color value L of polyetheretherketone * is (81.15~88.26). This gives a white polyether ether ketone.

[0053] In the embodiment of the present invention, the color value (L * ) and tensile strength (Rm * ) is in the range of 9975 ≧ Rm*L* ≧ 5100. This improves the properties of polyetheretherketone.

[0054] Another aspect of the present invention provides a solid polyetheretherketone. The solid polyetheretherketone is produced by the above-described method, and therefore has all the characteristics and advantages of the polyetheretherketone produced by the above-described method, and further description thereof will be omitted here. Generally, the chromaticity value L * It has at least the advantages of being high in viscosity and white in colour.

[0055] The present invention will be described below based on specific examples of the present invention. Unless specific techniques or conditions are specified in the examples, they will be in accordance with the techniques and conditions described in the literature in this field or in accordance with the product specifications. Unless the manufacturer is specified, the reagents or equipment used are all commercially available ordinary products.

[0056] Characteristics Test About the color test method The sample was injection molded into a standard color sample plate at 380°C, and the color value L was measured using a colorimeter. * Measure.

[0057] Tensile strength After injection molding into a standard test sample plate using an injection molding machine, the tensile strength of the sample was determined using a Shimadzu AG-Xplus universal testing machine in accordance with ISO 527. The test method was as follows: first, the sample was injection molded into a standard test sample plate using an injection molding machine, and then cut into 50 x 4 mm sample strips using a mold. Both ends of the sample strip were fixed into the tensile mold of the universal testing machine at a tensile speed of 2 mm / min. The test was repeated three times for each sample and the average value was calculated.

[0058] Viscosity Reduced viscosity (RV) is measured in concentrated sulfuric acid (1 wt.% / vol) at 25°C according to ASTM D2857-95(2007). The viscometer tube is a #50 Cannon Fenske. The solution used is prepared by dissolving 1.0000 ± 0.0004 g of resin in 100 ml ± 0.3 ml of concentrated sulfuric acid (95%-98%, density = 1.84). The concentration C in g / dL is equal to the weight (g) of polymer divided by the volume (dL) (100 ml = 1 dL). To facilitate this dissolution, a ground powder (approximately 200-600 μm average particle size) is used. The sample is dissolved at room temperature (without heating).

[0059] Filter the solution through a glass frit (medium porosity) before use. Calculate the RV as shown in the following formula:

number

[0060] where t 溶液 and t 溶媒 are the efflux times measured for the solution and the blank solvent, respectively. The efflux time is the average of at least three measurements. Under these conditions, the efflux time should be longer than 200 s without kinetic energy correction.

[0061] Since sulfonation of the polymer may occur in concentrated sulfuric acid, the effluent time of the solution must be measured within 3 hours after preparation.

[0062] The purity of hydroquinone in the following examples is 99.5% or higher, with the highest purity reaching 99.9%.

[0063] Example 1 A 500ml four-neck flask was charged with 300g of hydroquinone, a stirrer inserted through the middle neck, a three-way pipe inserted through one side neck, a thermometer and argon gas inlet connected to each, a vent pipe inserted through the other side neck to the bottom of the flask, and an Allen condenser connected to one side neck as an outlet. The flask was placed in an electric heating mantle, and high-purity argon gas was introduced into the flask through the two inlet side necks at a flow rate of 50ml / min (min). The purity of the argon gas was ≥ 99.999%. Heat until the hydroquinone melts, adjust the flow rate of argon gas to 200 ml / min, start stirring and increase the rotation speed to 80 rpm, maintain the temperature of the molten hydroquinone at 178°C, continue the reaction for 1 hour, place the four-necked flask containing the molten hydroquinone in a heated oil bath and cool to room temperature, stop the introduction of argon gas, obtain a complex of hydroquinone and argon gas, remove the hydroquinone complex from the flask and weigh it to be 301.12 g.

[0064] Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 110.51g of hydroquinone complex into a three-necked flask, introduce high-purity argon gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder.

[0065] Example 2 A 500ml four-neck flask was charged with 300g of hydroquinone, a stirring rod inserted through the middle neck of the flask, a three-way pipe inserted into one side neck, a thermometer and argon gas inlet connected to the three-way pipe, a vent pipe inserted into the bottom of the other side neck, and an Allen condenser connected to the other side neck as an outlet. The flask was placed in an electric heating mantle, and high-purity argon gas was introduced into the flask through the two inlet side necks at a flow rate of 50ml / min and a purity of 99.999% or higher. Heat until the hydroquinone melts, adjust the flow rate of argon gas to 200 ml / min, start stirring and increase the rotation speed to 80 rpm, maintain the temperature of the molten hydroquinone at 188 °C, continue the reaction for 1 hour, place the four-necked flask containing the molten hydroquinone in a heated oil bath and cool to room temperature, stop the introduction of argon gas, obtain a complex of hydroquinone and argon gas, remove the hydroquinone complex from the flask and weigh it to be 301.66 g.

[0066] Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 110.71g of hydroquinone complex into a three-necked flask, introduce high-purity argon gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder.

[0067] Example 3 A 500ml four-neck flask was charged with 300g of hydroquinone, a stirring rod inserted through the middle neck of the flask, a three-way pipe inserted into one side neck, a thermometer and argon gas inlet connected to the three-way pipe, a vent pipe inserted into the bottom of the other side neck, and an Allen condenser connected to the other side neck as an outlet. The flask was placed in an electric heating mantle, and high-purity argon gas was introduced into the flask through the two inlet side necks at a flow rate of 50ml / min and a purity of 99.999% or higher. Heat until the hydroquinone melts, adjust the flow rate of argon gas to 200 ml / min, start stirring and increase the rotation speed to 80 rpm, maintain the temperature of the molten hydroquinone at 198°C, continue the reaction for 1 hour, place the four-necked flask containing the molten hydroquinone in a heated oil bath and cool to room temperature, stop the introduction of argon gas, obtain a complex of hydroquinone and argon gas, remove the hydroquinone complex from the flask and weigh it to be 301.95 g.

[0068] A three-neck flask was charged with 521.34 g of diphenyl sulfone, 218.2 g of 4,4'-difluorobenzophenone, 121.89 g of sodium carbonate, and 110.82 g of the hydroquinone complex of Example 1. High-purity argon gas was introduced and the mixture was heated until melted. Stirring was started, the rotation speed was increased to 60 rpm, the temperature was raised to 200°C and maintained for 1 hour, then heated to 280°C and maintained for 1 hour, then heated to 305°C and maintained at that temperature for 2 hours while reacting. The material was then added to cold distilled water to obtain a white mass. The white mass was crushed and washed 5-6 times with ethanol to remove the diphenyl sulfone solvent, and washed 5-6 times with distilled water to remove the sodium fluoride produced in the reaction, yielding a white powder.

[0069] Example 4 A 500ml four-neck flask was charged with 300g of hydroquinone, a stirring rod inserted through the middle neck of the flask, a three-way pipe inserted into one side neck, a thermometer and argon gas inlet connected to the three-way pipe, a vent pipe inserted into the bottom of the other side neck, and an Allen condenser connected to the other side neck as an outlet. The flask was placed in an electric heating mantle, and high-purity argon gas was introduced into the flask through the two inlet side necks at a flow rate of 50ml / min and a purity of 99.999% or higher. Heat until the hydroquinone melts, adjust the flow rate of argon gas to 200 ml / min, start stirring and increase the rotation speed to 80 rpm, maintain the temperature of the molten hydroquinone at 208 ° C, continue the reaction for 1 hour, place the four-necked flask containing the molten hydroquinone in a heated oil bath and cool to room temperature, stop the introduction of argon gas, obtain a complex of hydroquinone and argon gas, remove the hydroquinone complex from the flask and weigh it to be 302.37 g.

[0070] Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 110.97g of hydroquinone complex into a three-necked flask, introduce high-purity argon gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder.

[0071] Example 5 A 500ml four-neck flask was charged with 300g of hydroquinone, a stirring rod inserted through the middle neck of the flask, a three-way pipe inserted into one side neck, a thermometer and argon gas inlet connected to the three-way pipe, a vent pipe inserted into the bottom of the other side neck, and an Allen condenser connected to the other side neck as an outlet. The flask was placed in an electric heating mantle, and high-purity argon gas was introduced into the flask through the two inlet side necks at a flow rate of 50ml / min and a purity of 99.999% or higher. Heat until the hydroquinone melts, adjust the flow rate of argon gas to 200 ml / min, start stirring and increase the rotation speed to 80 rpm, maintain the temperature of the molten hydroquinone at 218°C, continue the reaction for 1 hour, place the four-necked flask containing the molten hydroquinone in a heated oil bath and cool to room temperature, stop the introduction of argon gas, obtain a complex of hydroquinone and argon gas, remove the hydroquinone complex from the flask and weigh it to be 305.40 g.

[0072] Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 112.09g of hydroquinone complex into a three-necked flask, introduce high-purity argon gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder.

[0073] Example 6 A 500ml four-neck flask was charged with 300g of hydroquinone, a stirring rod inserted through the middle neck of the flask, a three-way pipe inserted into one side neck, a thermometer and argon gas inlet connected to the three-way pipe, a vent pipe inserted into the bottom of the other side neck, and an Allen condenser connected to the other side neck as an outlet. The flask was placed in an electric heating mantle, and high-purity argon gas was introduced into the flask through the two inlet side necks at a flow rate of 50ml / min and a purity of 99.999% or higher. Heat until the hydroquinone melts, adjust the flow rate of argon gas to 200 ml / min, start stirring and increase the rotation speed to 80 rpm, maintain the temperature of the molten hydroquinone at 228 ° C, continue the reaction for 1 hour, place the four-necked flask containing the molten hydroquinone in a heated oil bath and cool to room temperature, stop the introduction of argon gas, obtain a complex of hydroquinone and argon gas, remove the hydroquinone complex from the flask and weigh it to be 313.52 g.

[0074] Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 115.07g of hydroquinone complex into a three-necked flask, introduce high-purity argon gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder.

[0075] Example 7 A 500ml four-neck flask was charged with 300g of hydroquinone, a stirring rod inserted through the middle neck of the flask, a three-way pipe inserted into one side neck, a thermometer and argon gas inlet connected to the three-way pipe, a vent pipe inserted into the bottom of the other side neck, and an Allen condenser connected to the other side neck as an outlet. The flask was placed in an electric heating mantle, and high-purity argon gas was introduced into the flask through the two inlet side necks at a flow rate of 50ml / min and a purity of 99.999% or higher. Heat until the hydroquinone melts, adjust the flow rate of argon gas to 200 ml / min, start stirring and increase the rotation speed to 80 rpm, maintain the temperature of the molten hydroquinone at 238°C, continue the reaction for 1 hour, place the four-necked flask containing the molten hydroquinone in a heated oil bath and cool to room temperature, stop the introduction of argon gas, obtain a complex of hydroquinone and argon gas, remove the hydroquinone complex from the flask and weigh it to be 307.45 g.

[0076] Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 112.84g of hydroquinone complex into a three-necked flask, introduce high-purity argon gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder.

[0077] Example 8 A 500ml four-neck flask was charged with 300g of hydroquinone, a stirring rod inserted through the middle neck of the flask, a three-way pipe inserted into one side neck, a thermometer and argon gas inlet connected to the three-way pipe, a vent pipe inserted into the bottom of the other side neck, and an Allen condenser connected to the other side neck as an outlet. The flask was placed in an electric heating mantle, and high-purity argon gas was introduced into the flask through the two inlet side necks at a flow rate of 50ml / min and a purity of 99.999% or higher. Heat until the hydroquinone melts, adjust the flow rate of argon gas to 200 ml / min, start stirring and increase the rotation speed to 80 rpm, maintain the temperature of the molten hydroquinone at 248 ° C, continue the reaction for 1 hour, place the four-necked flask containing the molten hydroquinone in a heated oil bath and cool to room temperature, stop the introduction of argon gas, obtain a complex of hydroquinone and argon gas, remove the hydroquinone complex from the flask and weigh it to be 300.22 g.

[0078] Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 110.18g of hydroquinone complex into a three-necked flask, introduce high-purity argon gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder.

[0079] Comparative Example 1 Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 110.1g of hydroquinone into a three-necked flask, introduce high-purity argon gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder.

[0080] Comparative Example 2 Add 521.34g of diphenylsulfone, 218.2g of 4,4'-difluorobenzophenone, 121.89g of sodium carbonate and 110.1g of hydroquinone complex into a three-necked flask, introduce high-purity nitrogen gas, heat until melted, start stirring, increase the rotation speed to 60 rpm, raise the temperature to 200°C and maintain for 1 hour, then heat to 280°C and maintain for 1 hour, raise the temperature to 305°C and maintain this temperature for 2 hours while reacting, add the material to cold distilled water to obtain white lumps, crush the white lumps, wash with ethanol 5-6 times to remove the diphenylsulfone solvent, wash with distilled water 5-6 times to remove the sodium fluoride produced in the reaction, and obtain a white powder. TIFF0007751086000002.tif83170

[0081] As can be seen from Examples 1 to 8, in the process of producing the hydroquinone complex, the input raw materials were all 300 g, and the weight of the product was all greater than 300 g, so it can be determined that hydroquinone and argon gas produce the hydroquinone complex.

[0082] Comparing Examples 1 to 8, the yield of the hydroquinone complex produced at different temperatures differs. As the temperature increases, the yield of the hydroquinone complex increases, the yield is highest at 280°C, and then the yield decreases as the temperature increases. Comparing Examples 1 to 8 with Comparative Examples 1 and 2, the color value L of the polyether ether ketone produced with the hydroquinone complex is * is larger, i.e. the resulting solid polyetheretherketone is whiter.

[0083] Comparing Examples 1 to 8 with Comparative Example 2, the hydroquinone in the reactant during the nucleophilic substitution reaction was a hydroquinone complex containing an Ar atom, and the inert gas in Examples 1 to 8 was argon gas, while the inert gas in Comparative Example 2 was nitrogen gas. As can be seen from Table 1, the color value L of the polyether ether ketone produced in Comparative Example 2 was *is low, which indicates that when the inert gas in the nucleophilic substitution reaction process is argon gas, it can further prevent hydroquinone from being oxidized to some extent.

[0084] In the description herein, references to terms such as "one embodiment," "an embodiment," "example," "specific example," "an example," and the like mean that the specific features, structures, materials, or characteristics described in combination with the embodiment or example are included in at least one embodiment or example of the present invention. In the description herein, the exemplary expressions of the above terms are not necessarily limited to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be appropriately combined in any one or more embodiments or examples. Furthermore, if not mutually inconsistent, a person skilled in the art may combine or combine different embodiments or examples and features of different embodiments or examples described herein.

[0085] While embodiments of the present invention have been shown and described above, it should be understood that the above embodiments are illustrative and should not be construed as limiting the present invention, and that those skilled in the art may make changes, modifications, variations and variations to the above embodiments within the scope of the present invention. [Industrial Applicability]

[0086] The polyether ether ketone produced by the method for producing polyether ether ketone according to the present invention has a chromaticity value (L * ) and white color, which can be applied to certain electronic fields, such as the manufacture of wafer carriers, electronic insulating films, etc.

Claims

1. A method for producing a complex of hydroquinone or biphenol, comprising: introducing argon gas into a vessel containing hydroquinone or biphenol; mixing difluorobenzophenone, an alkali metal carbonate, a complex of hydroquinone or biphenol, and a solvent, and subjecting the mixture to a temperature programming process to produce polyetheretherketone; The elevated temperature programming process includes: elevating the temperature of the mixture of difluorobenzophenone, alkali metal carbonate, hydroquinone or biphenol complex, and solvent to a second predetermined temperature to obtain a first solution; raising and maintaining the temperature of the first solution at a third predetermined temperature to obtain a second solution; and heating and maintaining the second solution at a fourth predetermined temperature to obtain a third solution; the second predetermined temperature is between 190°C and 210°C; the third predetermined temperature is between 270°C and 290°C; The fourth predetermined temperature is 300°C to 320°C.

2. The complex comprises an Ar atom, and the formation of the complex is introducing argon gas into a vessel containing hydroquinone or biphenol at a flow rate of 20 to 100 ml / min and heating the vessel to melt the hydroquinone or biphenol; increasing the flow rate of the argon gas to 150-250 ml / min, and heating and maintaining the hydroquinone or biphenol at a first predetermined temperature to obtain a complex of hydroquinone or biphenol; The method of claim 1, wherein the first predetermined temperature is between 178°C and 248°C.

3. The method described in claim 2, wherein after hydroquinone or biphenol has melted, argon gas is continuously introduced under stirring conditions, and the rotation speed during stirring is 70 to 100 rpm.

4. The method of claim 1, wherein the purity of the argon gas is between 80% and 100%.

5. 10. The method of claim 1, wherein the ramp-up programming process is performed under inert gas protection and further comprises heating the mixture until the mixture melts before ramping the mixture to a second predetermined temperature.

6. The method described in claim 1, wherein the purity of the hydroquinone is 90% to 99.9%.

7. 7. The method of claim 6, wherein the purity of the hydroquinone is 98% to 99.9%.

8. The difluorobenzophenone includes at least one of 4,4'-difluorobenzophenone, 3,4'-difluorobenzophenone, and 2,4'-difluorobenzophenone; The alkali metal carbonate includes one or two of sodium carbonate, potassium carbonate, strontium carbonate, and cesium carbonate; the solvent comprises at least one of sulfolane, diphenyl sulfone, dimethyl sulfoxide, and methyl pyrrolidone; 2. The method according to claim 1, wherein the molar ratio of hydroquinone or biphenol, difluorobenzophenone and alkali metal carbonate is (1-1.2):1:(1-1.1).

9. The method according to claim 1, further comprising the step of subjecting the mixed solution containing polyetheretherketone to a separation and purification treatment to obtain solid polyetheretherketone.

10. Chromaticity value of polyether ether ketone (L ＊ 2. The method of claim 1, wherein the .alpha.-to- ...

11. Chromaticity value of polyether ether ketone (L ＊ ) and tensile strength (Rm ＊ 2. The method of claim 1, wherein the range of the product of Rm*L* and Rm*L* is 9975≧Rm*L*≧5100.

12. The method of claim 5 , wherein the inert gas is argon gas.

13. 13. A solid polyetheretherketone produced by the method of any one of claims 1 to 11 or claim 12, comprising: The chromaticity value (L*) of the polyether ether ketone is (81.15 to 88.26), A solid polyetheretherketone, wherein the range of the product of the color value (L*) and the tensile strength (Rm) of the polyetheretherketone is 9975≧Rm*L*≧5100.

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