A copolymer polyether ketone ultra-thin film raw material and a preparation method thereof, a copolymer polyether ketone ultra-thin film and a preparation method thereof, and application in the field of acoustic diaphragms

Abstract

The application belongs to the technical field of polymer materials and its preparation, and particularly relates to a copolymer polyether ketone ultra-thin film raw material and a preparation method thereof, a copolymer polyether ketone ultra-thin film and a preparation method thereof and application thereof in the field of acoustic diaphragms. The copolymer polyether ketone ultra-thin film raw material provided by the application is reasonable in compatibility, low in cost and easy to obtain. The copolymer polyether ketone ultra-thin film provided by the application is prepared from the copolymer polyether ketone ultra-thin film raw material described in the above scheme, and is endowed with excellent high-temperature resistance and high toughness, outstanding high-temperature wear resistance and excellent comprehensive performance. The application also provides application of the copolymer polyether ketone ultra-thin film described in the above scheme or the copolymer polyether ketone ultra-thin film obtained by the preparation method described in the above scheme in the field of acoustic diaphragms. The copolymer polyether ketone ultra-thin film provided by the application has excellent high-temperature resistance and high toughness, and is suitable for use in the field of acoustic diaphragms.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer materials and its preparation, and particularly relates to a copolymer polyether ketone ultra-thin film raw material and a preparation method thereof, a copolymer polyether ketone ultra-thin film and a preparation method thereof and application thereof in the field of acoustic diaphragms. BACKGROUND

[0002] Polyether ketone is a high polymer with a main chain formed by alternating ether bonds and ketone bonds. As a kind of polyaryletherketone, polyether ketone is widely used due to its high performance. It has excellent mechanical properties, corrosion resistance, high temperature resistance and electrical insulation properties, and exhibits excellent durability in extremely harsh environments.

[0003] However, with the development of production and life, the application scenarios of polyether ketone are continuously expanding, and it is often used in high-temperature harsh environments. The high-temperature resistance and toughness of polyaryletherketone have become a short board restricting its application. SUMMARY

[0004] The purpose of the present application is to provide a copolymer polyether ketone ultra-thin film raw material and a preparation method thereof, a copolymer polyether ketone ultra-thin film and a preparation method thereof and application thereof in the field of acoustic diaphragms. The copolymer polyether ketone ultra-thin film raw material provided by the present application has excellent high-temperature resistance and toughness.

[0005] In order to achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0006] The present application provides a copolymer polyether ketone ultra-thin film raw material, which comprises, in mass parts, 100 parts of copolymer polyether ketone polymer, 2-6 parts of viscosity modifier resin, 0-1 part of thermal stabilizer and 0-2 parts of lubricant; the structure of the viscosity modifier resin is shown in formula I:

[0007]

[0008] In formula I, n is in the range of 10-60.

[0009] Preferably, the structure of the copolymer polyether ketone polymer is shown in formula A:

[0010]

[0011] In formula A, x=1-10%.

[0012] Preferably, the preparation method of the viscosity modifier resin comprises: mixing 4,4'-dihydroxybenzophenone, viscosity modifier resin monomer, water-carrying agent, catalyst and first solvent to sequentially perform azeotropic dehydration reaction and polymerization reaction; the structure of the viscosity modifier resin monomer is shown in formula II:

[0013]

[0014] Preferably, the molar ratio of the viscosity modifier resin monomer to 4,4'-dihydroxybenzophenone is 1.0-1.25:1; the volume ratio of the water-carrying agent to the first solvent is 15-30:100; and the molar ratio of the catalyst to 4,4'-dihydroxybenzophenone is 1.0-1.5:1.

[0015] Preferably, the temperature of the azeotropic dehydration reaction is 160-180℃, and the holding reaction time is 1-3 hours; and the temperature of the polymerization reaction is 220-230℃, and the holding reaction time is 8-12 hours.

[0016] The application further provides a preparation method of the copolymerized polyether ketone ultra-thin film raw material.

[0017] The copolymerized polyether ketone polymer, the viscosity modifier resin, the thermal stabilizer, and the lubricant are mixed and dried to obtain a premix; and the premix is melt-extruded and granulated to obtain the copolymerized polyether ketone ultra-thin film raw material.

[0018] Preferably, the melt-extrusion is double-screw extrusion; the equipment used for the double-screw extrusion is a double-screw extruder; the front section of the barrel of the double-screw extruder has a temperature of 280-290℃, the middle section of the barrel has a temperature of 355-365℃, the rear end of the barrel has a temperature of 370-385℃, and the die has a temperature of 380-400℃; the screw rotation speed of the double-screw extrusion is 60-80rpm, and the screw feeding speed is 40-45rpm.

[0019] The application further provides a copolymerized polyether ketone ultra-thin film prepared from the copolymerized polyether ketone ultra-thin film raw material; the copolymerized polyether ketone ultra-thin film raw material is the copolymerized polyether ketone ultra-thin film raw material described in the above scheme or the copolymerized polyether ketone ultra-thin film raw material obtained by the preparation method described in the above scheme; and the thickness of the copolymerized polyether ketone ultra-thin film is 9-300μm.

[0020] The application further provides a preparation method of the copolymerized polyether ketone ultra-thin film described in the above scheme, including the following steps:

[0021] The copolymerized polyether ketone ultra-thin film raw material is cast formed to obtain the copolymerized polyether ketone ultra-thin film.

[0022] The application further provides an application of the copolymerized polyether ketone ultra-thin film described in the above scheme or the copolymerized polyether ketone ultra-thin film obtained by the preparation method described in the above scheme in the field of acoustic diaphragms.

[0023] The application provides a copolymerized polyether ketone ultra-thin film raw material. The copolymerized polyether ketone ultra-thin film raw material provided by the application is reasonably compatible, low in cost, and easy to obtain.

[0024] The application further provides a preparation method of the copolymer polyether ketone ultra-thin film raw material.

[0025] The application further provides a copolymer polyether ketone ultra-thin film.

[0026] The application further provides a preparation method of the copolymer polyether ketone ultra-thin film.

[0027] The application further provides an application of the copolymer polyether ketone ultra-thin film or the copolymer polyether ketone ultra-thin film prepared by the preparation method in the field of acoustic diaphragms. BRIEF DESCRIPTION OF DRAWINGS

[0028] In order to more clearly illustrate the technical solutions in the embodiments of the application or the prior art, the following will briefly introduce the drawings needed in the embodiments. Obviously, the drawings in the following description are only some embodiments of the application, and for those skilled in the art, other drawings can be obtained from these drawings without creative labor.

[0029] Figure 1 NMR spectrum of the viscosity regulator resin monomer prepared for Example 1;

[0030] Figure 2 DSC spectrum (left) and TGA spectrum (right) of the viscosity regulator resin;

[0031] Figure 3 Viscosity data of the copolymer polyether ketone ultra-thin film raw material of the 9 groups of formulations in Table 1;

[0032] Figure 4 Appearance photo of the copolymer polyether ketone ultra-thin film prepared in Example 4;

[0033] Figure 5 Infrared spectrum of the copolymer polyether ketone ultra-thin film prepared in Example 4;

[0034] Figure 6 Dynamic thermal mechanical property test diagram of the copolymer polyether ketone ultra-thin film prepared in Example 4;

[0035] Figure 7 Frequency response curve comparison diagram of the earphone core (top), receiver (middle) and loudspeaker (bottom) prepared in Application Examples 1-3 and AAC production line products. DETAILED DESCRIPTION

[0036] The application provides a copolymer polyether ketone ultra-thin film raw material, which contains 100 parts of copolymer polyether ketone polymer, 2-6 parts of viscosity modifier resin, 0-1 part of thermal stabilizer and 0-2 parts of lubricant in terms of mass fraction.

[0037] The copolymer polyether ketone ultra-thin film raw material provided by the application contains 100 parts of copolymer polyether ketone polymer; the copolymer polyether ketone polymer is preferably a polyether ketone polymer prepared according to Chinese patent CN110156981A; and the structure of the copolymer polyether ketone polymer is preferably shown in formula A:

[0038]

[0039] In formula A, x = 1-10%.

[0040] In terms of mass fraction of the copolymer polyether ketone polymer, the copolymer polyether ketone ultra-thin film raw material provided by the application contains 2-6 parts of viscosity modifier resin, which can be specifically 2 parts, 3 parts, 4 parts, 5 parts or 6 parts.

[0041] In the application, the structure of the viscosity modifier resin is shown in formula I:

[0042]

[0043] In formula I, the value range of n is 10-60.

[0044] In the application, the preparation method of the viscosity modifier resin is preferably as follows: 4,4'-dihydroxybenzophenone, viscosity modifier resin monomer, water-carrying agent, catalyst and first solvent are mixed (to obtain a first mixture) to sequentially perform azeotropic dehydration reaction and polymerization reaction.

[0045] In the application, the structure of the viscosity modifier resin monomer is shown in formula II:

[0046]

[0047] In the application, the preparation method of the viscosity modifier resin monomer is preferably as follows: 3,4',5-trifluorobenzophenone, phenol, potassium carbonate and a second solvent are mixed to perform a reflux reaction.

[0048] In the application, the molar ratio of 3,4',5-trifluorobenzophenone to phenol is preferably 1:0.9-1, and can be specifically 1:0.9, 1:0.92, 1:0.94, 1:0.96, 1:0.98 or 1:1.

[0049] In the present application, the molar ratio of the 3,4',5-trifluorobenzophenone to potassium carbonate is preferably 1:1-1.3, and can be 1:1, 1:1.1, 1:1.2 or 1:1.3 in particular.

[0050] In the present application, the second solvent is preferably N,N-dimethylacetamide (DMAc).

[0051] In the present application, the molar ratio of the 3,4',5-trifluorobenzophenone to the second solvent is preferably 1:45-55, and can be 1:45, 1:50 or 1:55 in particular.

[0052] In the present application, the temperature of the reflux reaction is preferably 160-165℃, and the holding reaction time is preferably 2-5 hours, and can be 2 hours, 3 hours, 4 hours or 5 hours in particular; the chemical reaction equation of the reflux reaction is as follows:

[0053]

[0054] In the present application, the reflux reaction is preferably carried out in an inert atmosphere; the inert atmosphere preferably includes one or both of nitrogen and argon.

[0055] In the present application, the reflux reaction is preferably followed by sequentially carrying out precipitation, water washing, elution and drying (denoted as first drying) on the obtained reaction mixture.

[0056] In the present application, the precipitation is preferably: slowly pouring the reaction mixture into deionized water for precipitation, and collecting the precipitate; the water used for water washing is preferably hot deionized water; the temperature of the hot deionized water is preferably 90-100℃; the elution reagent is preferably dichloromethane; and the first drying is preferably oven drying; the temperature of the oven drying is preferably 50-65℃, and the holding drying time is preferably 3-6h.

[0057] In the present application, the molar ratio of the viscosity regulator resin monomer to 4,4'-dihydroxybenzophenone is preferably 1.0-1.25:1, and can be 1.0:1, 1.05:1, 1.1:1, 1.15:1, 1.2:1 or 1.25:1 in particular.

[0058] In the present application, the water-carrying agent is preferably a benzene homolog; the benzene homolog preferably includes one or more of toluene and xylene.

[0059] In the present application, the volume ratio of the water-carrying agent to the first solvent is preferably 15-30:100, and can be 15:100, 20:100, 25:100 or 30:100 in particular.

[0060] In the present application, the catalyst is preferably a carbonate; the carbonate preferably includes one or both of potassium carbonate (K2CO3) and sodium carbonate.

[0061] In the present application, the molar ratio of the catalyst to 4,4’-dihydroxybenzophenone is preferably 1.0-1.5:1, and can be 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1.

[0062] In the present application, the first solvent is preferably a sulfone; the sulfone is preferably tetramethylene sulfone (TMS).

[0063] In the present application, the solid content of the first mixture is preferably 15-30 wt%, and can be 15%, 20%, 25% or 30%.

[0064] In the present application, the temperature of the azeotropic dehydration reaction is preferably 160-180℃, and can be 160℃, 165℃, 170℃, 175℃ or 180℃, and the holding reaction time is preferably 1-3 hours, and can be 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours.

[0065] In the present application, the azeotropic dehydration reaction is preferably carried out under stirring; the stirring speed is preferably 75-100 rpm, and can be 85 rpm or 95 rpm; the azeotropic dehydration reaction is preferably carried out in an inert atmosphere; the inert atmosphere preferably includes one or both of nitrogen and argon.

[0066] In the present application, the azeotropic dehydration reaction is preferably followed by water removal from the obtained reaction system. The present application removes the water generated in the azeotropic dehydration reaction by water removal.

[0067] In the present application, the temperature of the polymerization reaction is preferably 220-230℃, and can be 220℃, 222℃, 224℃, 226℃, 228℃ or 230℃, and the holding reaction time is preferably 8-12 hours, and can be 8 hours, 9 hours, 10 hours, 11 hours or 12 hours; the chemical reaction equation of the azeotropic dehydration and polymerization reactions is as follows:

[0068]

[0069] In the present application, the polymerization reaction is preferably carried out under stirring; the stirring speed is preferably 230-250 rpm; the polymerization reaction is preferably carried out in an inert atmosphere; the inert atmosphere preferably includes one or both of nitrogen and argon.

[0070] In the present application, the polymerization reaction preferably further comprises heating the reaction system before the polymerization reaction; the heating rate is preferably 1-3℃ / min, and can be 1℃ / min, 2℃ / min or 3℃ / min; the heating is preferably carried out under stirring; the stirring speed is preferably 170-200rpm.

[0071] In the present application, the polymerization reaction preferably further comprises post-treatment after the polymerization reaction; the post-treatment preferably comprises: pouring the product (polymer solution) obtained from the polymerization reaction into water while hot to obtain a solid polymer, and then crushing the solid polymer and sequentially performing extraction, washing and drying (denoted as second drying).

[0072] In the present application, the water is preferably deionized water; the volume ratio of the polymer solution to the water is preferably not less than 1:8, and can be 1:8, 1:9, 1:10, 1:11 or 1:12.

[0073] In the present application, the reagent used for the extraction is preferably boiling ethanol; the extraction is preferably performed 4-10 times, and can be performed 4 times, 6 times, 8 times or 10 times.

[0074] In the present application, the water used for the washing is preferably boiling water; the boiling water is preferably deionized water boiled to boiling; the washing is preferably performed 4-10 times, and can be performed 4 times, 6 times, 8 times or 10 times.

[0075] In the present application, the second drying is preferably drying; the drying temperature is preferably 100-120℃, and can be 110℃; the heat preservation drying time is preferably 10-12h, and can be 11h.

[0076] In the present application, the copolymerized polyether ketone ultra-thin film raw material provided by the present application comprises 0-1 parts of a heat stabilizer based on the mass fraction of the copolymerized polyether ketone polymer, and can comprise 0 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts, 0.9 parts or 1 part.

[0077] In the present application, the heat stabilizer is preferably a commercially available heat stabilizer Doverphos S-9228.

[0078] In the present application, the copolymerized polyether ketone ultra-thin film raw material provided by the present application comprises 0-2 parts of a lubricant based on the mass fraction of the copolymerized polyether ketone polymer, and can comprise 0 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.7 parts, 0.9 parts, 1.2 parts, 1.5 parts, 1.8 parts or 2 parts.

[0079] In the present application, the lubricant is preferably a commercially available lubricant Dow Corning RM4-7081.

[0080] The application also provides a preparation method of the copolymer polyether ketone ultra-thin film raw material.

[0081] The copolymer polyether ketone polymer, the viscosity regulator resin, the thermal stabilizer and the lubricant are mixed and dried to obtain a premix;

[0082] The premix is melt-extruded and granulated to obtain the copolymer polyether ketone ultra-thin film raw material.

[0083] The copolymer polyether ketone polymer, the viscosity regulator resin, the thermal stabilizer and the lubricant are mixed (denoted as first mixing) and dried (denoted as third drying) to obtain a premix. In the application, the first mixing time is preferably 0.5-1.5 h, and can be 0.5 h, 0.7 h, 0.9 h, 1.0 h, 1.1 h, 1.3 h or 1.5 h; and the first mixing device is preferably a planetary mixer.

[0084] In the application, the third drying is preferably drying by baking; the baking temperature is preferably 100-200℃, and can be 100℃, 120℃, 140℃, 160℃, 180℃ or 200℃; and the heat preservation drying time is preferably 3-8 hours, and can be 3 hours, 4 hours, 5 hours, 6 hours, 7 hours or 8 hours.

[0085] After obtaining the premix, the premix is melt-extruded and granulated to obtain the copolymer polyether ketone ultra-thin film raw material. In the application, the melt-extrusion is double-screw extrusion; the double-screw extrusion device is preferably a double-screw extruder; the double-screw extruder is preferably preheated before use; and the target temperature of the preheating is preferably 380-400℃, and can be 390℃.

[0086] In the application, the front barrel temperature of the double-screw extruder is preferably 280-290℃, and can be 280℃, 284℃, 287℃ or 290℃; the middle barrel temperature is preferably 355-365℃, and can be 355℃, 358℃, 361℃ or 365℃; the rear barrel temperature is preferably 370-385℃, and can be 375℃ or 380℃; the die temperature is preferably 380-400℃, and can be 380℃, 385℃, 390℃, 395℃ or 400℃.

[0087] In the application, the screw rotation speed of the double-screw extrusion is preferably 60-80 rpm, and can be 60 rpm, 65 rpm, 70 rpm, 75 rpm or 80 rpm; and the screw feeding speed is preferably 40-45 rpm, and can be 43 rpm. The application ensures that the raw material is sufficiently plasticized and uniformly mixed through double-screw extrusion, and the mixed material is extruded from the die and shaped by the die.

[0088] In the present application, the melt extrusion preferably further comprises cooling the product; the cooling is preferably water cooling; the final temperature of the cooling is preferably room temperature.

[0089] In the present application, the target particle size of the granulation is preferably 0.5-1 cm.

[0090] The present application also provides a copolymer polyether ketone ultra-thin film prepared from the copolymer polyether ketone ultra-thin film raw material; the copolymer polyether ketone ultra-thin film raw material is the copolymer polyether ketone ultra-thin film raw material described in the above scheme or the copolymer polyether ketone ultra-thin film raw material obtained by the preparation method described in the above scheme; the thickness of the copolymer polyether ketone ultra-thin film is 9-300 μm.

[0091] In the present application, the thickness of the copolymer polyether ketone ultra-thin film is preferably 9-290 μm, and specifically can be 9 μm, 10 μm, 20 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm or 290 μm.

[0092] In the present application, the width of the copolymer polyether ketone ultra-thin film is preferably 10-100 cm, and specifically can be 10 cm, 20 cm, 40 cm, 60 cm, 80 cm or 100 cm.

[0093] The present application also provides a preparation method of the copolymer polyether ketone ultra-thin film described in the above scheme, comprising the following steps:

[0094] The copolymer polyether ketone ultra-thin film raw material is cast formed to obtain the copolymer polyether ketone ultra-thin film.

[0095] In the present application, the equipment used for the cast forming is preferably an extruder; the temperature of the feeding section of the extruder is preferably 330-350℃, and specifically can be 330℃, 335℃, 340℃, 345℃ or 350℃, the temperature of the compression section is preferably 395-405℃, and specifically can be 395℃, 400℃ or 405℃, the temperature of the homogenization section is preferably 405-415℃, and specifically can be 405℃, 410℃ or 415℃, the temperature of the extrusion die is preferably 395-405℃, and specifically can be 395℃, 400℃ or 405℃, the temperature of the melt pump is preferably 395-405℃, and specifically can be 395℃, 400℃ or 405℃, the temperature of the filter screen is preferably 395-405℃, and specifically can be 395℃, 400℃ or 405℃, and the temperature of the hot roller is preferably 155-165℃, and specifically can be 155℃, 160℃ or 165℃.

[0096] In the present application, the screw torque of the extruder is preferably 60-80 Nm, and can be 60 Nm, 65 Nm, 70 Nm, 75 Nm or 80 Nm in particular, the screw feeding speed is preferably 40-45 rpm, and can be 43 rpm in particular, and the screw rotation speed is preferably 60-80 rpm, and can be 60 rpm, 65 rpm, 70 rpm, 75 rpm or 80 rpm in particular.

[0097] In the present application, the casting forming preferably further comprises winding the obtained formed product after the casting forming.

[0098] In the present application, the preparation of the copolymer polyether ketone ultra-thin film is preferably carried out in a dust-free experimental environment of 10000 or above.

[0099] The present application also provides the use of the copolymer polyether ketone ultra-thin film prepared by the preparation method in the field of acoustic diaphragms.

[0100] The copolymer polyether ketone ultra-thin film provided by the present application has excellent high-temperature resistance and high toughness, and is suitable for use in the field of acoustic diaphragms, and can be used in earphone cores, microphones or loudspeakers and the like.

[0101] In order to further illustrate the present application, the schemes of the present application are described in detail below in combination with the drawings and examples, but they should not be understood as limiting the scope of protection of the present application.

[0102] Example 1

[0103] (1) Preparation of viscosity modifier resin monomer:

[0104] 3,4',5-trifluorobenzophenone (7.08 g, 30 mmol), phenol (2.82 g, 30 mmol) and K2CO3 (4.35 g, 30 mmol) were added to 120 mL of DMAc, and heated to reflux under nitrogen protection for 3 hours to obtain a mixture, which was slowly poured into deionized water. The precipitate was collected and washed with hot deionized water (temperature 100℃) to obtain a crude product, which was eluted with dichloromethane and dried at 50℃ for 6 hours to obtain 6.96 g of the viscosity modifier resin monomer, a light yellow solid, and its nuclear magnetic resonance spectrum is shown in Figure 1 As can be seen, the viscosity modifier resin monomer is successfully prepared according to the present application, and the structure is shown in formula II. Figure 1

[0105] (2) Preparation of viscosity modifier resin:

[0106] ​Into a three-necked flask with mechanical stirring, argon inlet, water trap, 4,4'-dihydroxybenzophenone (6.42 g, 30 mmol), the viscosity modifier resin monomer (9.31 g, 30 mmol), water-carrying agent toluene (11.25 mL), and catalyst K2CO3(4.95 g, 36 mmol) were added into solvent TMS (37.5 mL), and the reaction was carried out at 170 °C under inert gas (nitrogen) protection with stirring at 100 rpm for 2 h, then the water generated in the reaction was removed, and the temperature was raised to 220 °C at a rate of 1 °C / min with stirring at 200 rpm, and the polymerization was carried out at 240 rpm for 10 h to obtain a polymer solution. The polymer solution was poured into a large amount of deionized water (the volume ratio of the polymer solution to deionized water was 1:8) while hot, and solid-liquid separation was performed to obtain a solid polymer powder, which was crushed, then extracted with boiling ethanol for 10 times, washed with boiling deionized water for 10 times, and dried at 110 °C for 11 h to obtain the viscosity modifier resin, the structure of which is shown in formula I, and the DSC spectrum and TGA spectrum thereof are shown in Figure 2 Figure 2 It can be seen that the glass transition temperature of the viscosity modifier resin is 128.7 °C, and the 5% thermal decomposition temperature is 494.0 °C, which proves that the viscosity modifier resin of the present application can stably exist in the subsequent granulation and film-making process.

[0107] (3) Preparation of copolymerized polyether ketone polymer:

[0108] Into a three-necked flask with mechanical stirring, argon inlet, water trap, 4,4'-dihydroxybenzophenone (6.42 g, 30 mmol), the viscosity modifier resin monomer (9.31 g, 30 mmol), water-carrying agent toluene (11.25 mL), and catalyst K2CO3(4.95 g, 36 mmol) were added into solvent TMS (37.5 mL), and the reaction was carried out at 170 °C under inert gas (nitrogen) protection with stirring at 100 rpm for 2 h, then the water generated in the reaction was removed, and the temperature was raised to 220 °C at a rate of 1 °C / min with stirring at 200 rpm, and the polymerization was carried out at 240 rpm for 10 h to obtain a polymer solution. The polymer solution was poured into a large amount of deionized water (the volume ratio of the polymer solution to deionized water was 1:8) while hot, and solid-liquid separation was performed to obtain a solid polymer powder, which was crushed, then extracted with boiling ethanol for 10 times, washed with boiling deionized water for 10 times, and dried at 110 °C for 11 h to obtain the viscosity modifier resin, the structure of which is shown in formula I, and the DSC spectrum and TGA spectrum thereof are shown in

[0109] Into a three-necked flask with mechanical stirring, argon inlet, water trap, 4,4'-dihydroxybenzophenone (6.42 g, 30 mmol), the viscosity modifier resin monomer (9.31 g, 30 mmol), water-carrying agent toluene (11.25 mL), and catalyst K2CO3(4.95 g, 36 mmol) were added into solvent TMS (37.5 mL), and the reaction was carried out at 170 °C under inert gas (nitrogen) protection with stirring at 100 rpm for 2 h, then the water generated in the reaction was removed, and the temperature was raised to 220 °C at a rate of 1 °C / min with stirring at 200 rpm, and the polymerization was carried out at 240 rpm for 10 h to obtain a polymer solution. The polymer solution was poured into a large amount of deionized water (the volume ratio of the polymer solution to deionized water was 1:8) while hot, and solid-liquid separation was performed to obtain a solid polymer powder, which was crushed, then extracted with boiling ethanol for 10 times, washed with boiling deionized water for 10 times, and dried at 110 °C for 11 h to obtain the viscosity modifier resin, the structure of which is shown in formula I, and the DSC spectrum and TGA spectrum thereof are shown in

[0110] (4) Preparation of copolymerized polyether ketone ultra-thin film raw material:

[0111] ​In mass parts, 100 parts of copolymerized polyether ketone polymer, 2 parts of viscosity modifier resin prepared in Example 1, 0 (or 0.05 or 0.1) parts of commercially available heat stabilizer Doverphos S-9228 and 0 (or 1 or 2) parts of commercially available lubricant Dow Corning RM4-7081 were mixed for 1 h using a planetary mixer, dried at 150°C for 4 h, and then fed into a twin-screw extruder preheated to 380°C, with the screw rotation speed (70 rpm), screw feeding speed (40 rpm), barrel temperature (280°C for the front section, 365°C for the middle section, and 385°C for the rear end), and die temperature (390°C) controlled, to obtain a mixture which was extruded from the die, granulated after being shaped by the die and cooled, to obtain copolymerized polyether ketone ultra-thin film raw material (denoted as copolymerized PEK).

[0112] Example 2

[0113] (1) Preparation of viscosity modifier resin:

[0114] 4,4'-dihydroxybenzophenone (6.42 g, 30 mmol), the viscosity modifier resin monomer (10.24 g, 33 mmol), water-carrying agent toluene (12.0 mL) and catalyst K2CO3 (5.39 g, 39 mmol) were added to solvent TMS (40.0 mL), and the reaction was carried out at 170°C under inert gas (nitrogen) protection with stirring at 100 rpm for 2 hours, the water generated in the reaction was removed, and then the temperature was raised to 220°C at a rate of 1°C / min while stirring at 200 rpm, and the polymerization reaction was carried out at 240 rpm for 10 hours to obtain a polymer solution. The polymer solution was poured into a large amount of deionized water (the volume ratio of the polymer solution to deionized water was 1:8) while hot, and solid-liquid separation was performed to obtain a solid polymer powder, which was crushed and then extracted with boiling ethanol for 10 times and washed with boiling deionized water for 10 times, and dried at 110°C for 11 h to obtain the viscosity modifier resin, the structure of which is shown in formula I.

[0115] (2) Preparation of copolymerized polyether ketone ultra-thin film raw material:

[0116] In mass parts, 100 parts of copolymerized polyether ketone polymer, 4 parts of viscosity modifier resin prepared in Example 1, 0 (or 0.05 or 0.1) parts of heat stabilizer and 0 (or 1 or 2) parts of lubricant were mixed for 1 h using a planetary mixer, dried at 150°C for 4 h, and then fed into a twin-screw extruder preheated to 390°C, with the screw rotation speed (70 rpm), screw feeding speed (40 rpm), barrel temperature (280°C for the front section, 365°C for the middle section, and 385°C for the rear end), and die temperature (390°C) controlled, to obtain a mixture which was extruded from the die, granulated after being shaped by the die and cooled, to obtain copolymerized polyether ketone ultra-thin film raw material (denoted as copolymerized PEK).

[0117] Example 3

[0118] (1) Preparation of viscosity modifier resin:

[0119] 4,4'-Dihydroxybenzophenone (6.42 g, 30 mmol), the viscosity modifier resin monomer (11.17 g, 36 mmol), toluene (12.6 mL) as a dehydrating agent, and K₂CO₃ (5.39 g, 39 mmol) as a catalyst were added to a solvent TMS (41.9 mL). The mixture was reacted at 170 °C and 100 rpm for 2 hours under inert gas (nitrogen) protection. Water generated during the reaction was removed. The temperature was then increased to 220 °C at a rate of 1 °C / min while stirring at 200 rpm. Polymerization was carried out at 240 rpm for 10 hours to obtain a polymer solution. The hot polymer solution was poured into a large amount of deionized water (polymer solution to deionized water volume ratio 1:8), and solid-liquid separation was performed to obtain a solid polymer powder. The solid polymer powder was pulverized, extracted 10 times with boiling ethanol, washed 10 times with boiling deionized water, and dried at 110 °C for 11 hours to obtain the viscosity modifier resin, with the structure shown in Formula I.

[0120] (2) Preparation of copolyetherketone ultrathin film raw materials:

[0121] By mass, using a planetary mixer, 100 parts of the copolyetherketone polymer, 6 parts of the viscosity modifier resin prepared in Example 1, 0 (or 0.05 or 0.1) parts of heat stabilizer and 0 (or 1 or 2) parts of lubricant were mixed for 1 hour, dried at 150°C for 4 hours, and then added to a twin-screw extruder preheated to 400°C. The screw speed (70 rpm), screw feed rate (40 rpm), barrel temperature (front section 280°C, middle section 365°C, rear section 385°C), and die temperature (390°C) were controlled. The resulting mixture was extruded from the die, shaped by the die, cooled, cured, and granulated to obtain the copolyetherketone ultrathin film raw material (denoted as copoly PEK).

[0122] Table 1. Nine formulations (parts by weight) of polyetherketone ultrathin film raw materials in Examples 1-3.

[0123]

[0124]

[0125] The viscosity of the copolyetherketone ultrathin film raw materials of the nine formulations in Table 1 was tested, and the results are as follows: Figure 3 As shown. According to Figure 3 It can be seen that viscosity modifiers effectively reduce the processing viscosity of resins, and the shear viscosity decreases more significantly with the increase of viscosity modifier content; moreover, the addition of heat stabilizers further reduces the viscosity of the material, especially at low shear rates, where the effect of viscosity modifiers is obvious.

[0126] Example 4

[0127] The preparation method of the copolymerized polyether ketone ultra-thin film in the present example comprises the following steps:

[0128] The copolymerized polyether ketone ultra-thin film raw material is cast to form the copolymerized polyether ketone ultra-thin film; the temperature of the feeding section of the extruder is controlled at 350℃, the temperature of the compression section is controlled at 400℃, the temperature of the homogenization section is controlled at 410℃, the temperature of the melt pump and the filter screen is controlled at 400℃, the temperature of the extrusion die is controlled at 400℃, the screw torque is 70 Nm, the screw feeding speed is 40 rpm, the screw rotation speed is 70 rpm, and the hot roller temperature is 160℃; under the condition that the feeding speed and the heating temperature of each section are constant, the thickness of the copolymerized polyether ketone ultra-thin film is regulated by the pulling speed (5 m / min); after forming, the copolymerized polyether ketone ultra-thin film is wound up, and the copolymerized polyether ketone ultra-thin film with a thickness of 15 μm and a film width of 10.6 cm is obtained, and the appearance thereof is as shown in FIG. 1. Figure 4 As can be seen, the appearance has good transparency. Figure 4

[0129] The copolymerized polyether ketone ultra-thin film prepared in the present example is subjected to infrared spectrum analysis, and the results are as shown in FIG. 2. Figure 5 As can be seen, the peak at 1649 cm -1 is the stretching vibration peak of C=O in the polyether ketone molecule; the peak at 1234 cm -1 is the stretching vibration absorption peak of Ar-O-Ar (Ar is aryl) in the polyether ketone molecule, which proves that the copolymerized polyether ketone ultra-thin film prepared in the present example has the same structure as the pure polyether ketone. Figure 5 The copolymerized polyether ketone ultra-thin film prepared in the present example is subjected to dynamic thermal mechanical property test, and the results are as shown in FIG. 3.

[0130] As can be seen, the glass transition temperature of the copolymerized polyether ketone film prepared in the present example reaches 159℃, which is about 15℃ higher than that of the ordinary polyaryletherketone material (such as polyether ether ketone material), which indicates that the film material provided by the present application has stronger high-temperature resistance and higher use temperature. Figure 6 Figure 6 The mechanical properties of the copolymerized polyether ketone ultra-thin film prepared in the present example are tested, and the results are as shown in Table 2.

[0131] Table 2: Mechanical property test results of the copolymerized polyether ketone ultra-thin film

[0132] Table 2: Mechanical property test results of the copolymerized polyether ketone ultra-thin film

[0133]

[0134]

[0135] ​​According to Table 2, the copolymer polyether ketone ultra-thin film prepared in the embodiment has a tensile strength of 100±2 MPa and an elongation at break of 194%, which proves that the copolymer polyether ketone ultra-thin film has good mechanical strength and toughness.

[0136] Application Example 1

[0137] Acoustic diaphragm application: earphone core preparation and performance test

[0138] The earphone core product was obtained by assembling after pressing film with the 9 μm single-layer copolymer PEK film, and the frequency response (SPL) curve was tested, and the results are shown in the upper part of Figure 7 It can be seen that the SPL curve of the earphone core product assembled by the copolymer polyether ketone ultra-thin film of the application is close to that of the AAC earphone core product, but the standard deviation is greater than that of the AAC product.

[0139] Application Example 2

[0140] Acoustic diaphragm application: microphone preparation and performance test

[0141] The microphone product was obtained by pressing film after manually laminating the 9 μm copolymer PEK-gel-TPU, and the SPL curve was tested, and the results are shown in the middle part of Figure 7 It can be seen that the SPL curve of the microphone product assembled by the copolymer polyether ketone ultra-thin film of the application is significantly lower than that of the AAC product in the low frequency region.

[0142] Application Example 3

[0143] Acoustic diaphragm application: loudspeaker preparation and performance test

[0144] The copolymer PEK (9 μm)-silica gel-PEEK (5 μm) was laminated, and the lamination was flat and bubble-free; the loudspeaker product was obtained by pressing film after lamination, and the SPL curve was tested, and the results are shown in the lower part of Figure 7 It can be seen that the SPL curve of the loudspeaker product of the copolymer polyether ketone ultra-thin film of the application is slightly lower than that of the AAC product in the low frequency region.

[0145] As can be seen from the above embodiments, the copolymer polyether ketone ultra-thin film provided by the application has excellent high temperature resistance and high toughness, and outstanding high temperature wear resistance.

[0146] Although the above embodiments have made a detailed description of the application, it is only a part of the embodiments of the application, not all the embodiments, and other embodiments can be obtained under the premise of no creativity according to the embodiments, which all belong to the protection scope of the application.

Claims

1. A copolymer polyether ketone ultra-thin film feedstock, characterized by, comprising copolymerized polyether ketone polymer 100 parts by mass, viscosity modifier resin 2-6 parts by mass, thermal stabilizer 0-1 part by mass and lubricant 0-2 parts by mass; The structure of the viscosity modifier resin is shown as formula I: In formula I, n is 10-60.

2. The copolymerized polyetherketone ultra-thin film feedstock according to claim 1, characterized in that, The structure of the copolymerized polyether ketone polymer is shown as formula A: In formula A, x = 1-10%.

3. The copolymerized polyetherketone ultra-thin film feedstock according to claim 1, characterized in that, The viscosity modifier resin is prepared by mixing 4,4'-dihydroxybenzophenone, viscosity modifier resin monomer, water-carrying agent, catalyst and first solvent, and then carrying out azeotropic dehydration and polymerization reaction in sequence; The structure of the viscosity modifier resin monomer is shown as formula II:

4. The copolymerized polyetherketone ultra-thin film feedstock according to claim 3, characterized in that, The molar ratio of the viscosity modifier resin monomer to 4,4'-dihydroxybenzophenone is 1.0-1.25:1; the volume ratio of the water-carrying agent to the first solvent is 15-30:100; and the molar ratio of the catalyst to 4,4'-dihydroxybenzophenone is 1.0-1.5:

1.

5. The copolymer polyetherketone ultra-thin film feedstock according to claim 3 or 4, characterized in that, The temperature of the azeotropic dehydration reaction is 160-180℃, and the holding reaction time is 1-3 hours; The temperature of the polymerization reaction is 220-230℃, and the holding reaction time is 8-12 hours.

6. The method of producing a copolymer polyether ketone ultra-thin film raw material according to any one of claims 1 to 5, characterized by, The steps include: The copolymerized polyether ketone polymer, viscosity modifier resin, thermal stabilizer and lubricant are mixed and then dried to obtain a premix; the premix is melt-extruded and then granulated to obtain the copolymerized polyether ketone ultra-thin film raw material.

7. The production method according to claim 6, wherein The melt-extrusion is double-screw extrusion; the equipment used for the double-screw extrusion is a double-screw extruder; the barrel front section temperature of the double-screw extruder is 280-290℃, the barrel middle section temperature is 355-365℃, the barrel rear end temperature is 370-385℃, and the die temperature is 380-400℃; the screw rotation speed of the double-screw extrusion is 60-80 rpm, and the screw feeding speed is 40-45 rpm.

8. A copolymeric polyetherketone ultra-thin film, characterized in that, The copolymerized polyether ketone ultra-thin film is prepared from the copolymerized polyether ketone ultra-thin film raw material; the copolymerized polyether ketone ultra-thin film raw material is the copolymerized polyether ketone ultra-thin film raw material of any one of claims 1-5 or the copolymerized polyether ketone ultra-thin film raw material prepared by the preparation method of any one of claims 6-7; and the thickness of the copolymerized polyether ketone ultra-thin film is 9-300 μm.

9. The method for preparing the copolyetherketone ultrathin film according to claim 8, characterized in that, The steps include: The copolymerized polyether ketone ultra-thin film is prepared from the copolymerized polyether ketone ultra-thin film raw material; the copolymerized polyether ketone ultra-thin film raw material is the copolymerized polyether ketone ultra-thin film raw material of any one of claims 1-5 or the copolymerized polyether ketone ultra-thin film raw material prepared by the preparation method of any one of claims 6-7; and the thickness of the copolymerized polyether ketone ultra-thin film is 9-300 μm. The steps include: The copolymerized polyether ketone ultra-thin film is prepared from the copolymerized polyether ketone ultra-thin film raw material; the copolymerized polyether ketone ultra-thin film raw material is the copolymerized polyether ketone ultra-thin film raw material of any one of claims 1-5 or the copolymerized polyether ketone ultra-thin film raw material prepared by the preparation method of any one of claims 6-7; and the thickness of the copolymerized polyether ketone ultra-thin film is 9-300 μm.

10. Use of the copolymerized polyether ketone ultra-thin film of claim 8 or the copolymerized polyether ketone ultra-thin film prepared by the preparation method of claim 9 in the field of acoustic diaphragms.

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