A preparation method and application of low-VOC polyetheretherketone

Abstract

The present invention provides a method for preparing low-VOC polyetheretherketone and a composite material using low-VOC polyetheretherketone as a main raw material, which relates to the field of polymer materials. The organic gas contained in the low-VOC polyetheretherketone of the present invention is fully discharged, and the diphenyl sulfone content thereof is reduced to about 2% by the headspace-GC-MS test method, so that the VOC index of the polyetheretherketone meets the requirements of the electronic cigarette field, and can also be used in medical implants, electronic and electrical fields that have strict requirements on material purity.

Description

Technical Field

[0001] The present invention relates to the field of chemical industry, in particular, to a method for preparing low-VOC polyetheretherketone and the application of low-VOC polyetheretherketone in the fields of electronic cigarettes and medical treatment, and in particular to preparing a composite material using polyetheretherketone as a main raw material. Background Art

[0002] Polyetheretherketone (PEEK) is a new type of semi-crystalline aromatic thermoplastic engineering plastic with excellent heat resistance, radiation resistance, chemical resistance, wear resistance, fatigue resistance and mechanical properties. It has replaced traditional materials such as metals and ceramics in many fields. At present, it has been widely used in aerospace, electronics, automobiles, energy, medical and other fields.

[0003] As the technology of the e-cigarette industry matures, e-cigarettes are becoming more and more popular. They are no longer niche or pure player products. In particular, with the emergence of more and more integrated small cigarettes and the birth of nicotine salt technology, e-cigarettes with small size, simple and convenient use, and low prices are increasingly accepted by smokers. E-cigarettes, like mobile phones, have gradually become mass consumer products. E-cigarettes also have very demanding requirements on materials, including dimensional stability, touch, mechanical properties, thermal insulation / thermal conductivity, and heat resistance. PEEK is the most perfect material and is used in the shell of electronic cigarettes, cartridge chambers, heating plate bases, atomization chambers and other parts.

[0004] VOC is the abbreviation of volatile organic compounds. In the ordinary sense, VOC refers to volatile organic compounds, but in the environmental sense, it refers to a class of active volatile organic compounds, that is, the type of volatile organic compounds that can cause harm. The VOC contained in polyetheretherketone is diphenyl sulfone. The existing polyetheretherketone raw materials for preparing electronic cigarettes need to be tested for VOC, because when the temperature of the electronic cigarette rises during use, the polyetheretherketone material will volatilize volatile organic compounds such as diphenyl sulfone, which are potentially harmful to the human body. Therefore, it is difficult to reduce the volatilization of harmful organic compounds in polyetheretherketone materials at high temperatures. Summary of the invention

[0005] The present invention aims to solve the technical problems in the background technology at least to a certain extent.

[0006] One aspect of the present invention provides a method for preparing low-VOC polyetheretherketone, comprising:

[0007] Step 1: Under the condition of continuous argon flow, hydroquinone calcium salt, diphenyl sulfone and 4,4'-difluorobenzophenone are heated to melt, stirred with a stirring paddle and continuously heated to 280°C, and diphenyl sulfone is slowly added again after reacting for 60 minutes. After the newly added diphenyl sulfone is melted, the reaction is continued at 280°C for 30 minutes, and the reactant is quickly poured into distilled water and continuously stirred to obtain polyetheretherketone crude particles;

[0008] Step 2: washing the crude polyetheretherketone particles with acetone for 4-8 times to remove the solvent diphenyl sulfone, then washing with a phosphoric acid-ethylenediaminetetraacetic acid composite solution to remove calcium fluoride, and finally washing the crude polyetheretherketone with distilled water for 4-8 times to obtain low-VOC polyetheretherketone;

[0009] Among them, the VOC content of low-VOC polyetheretherketone is 2%-10%.

[0010] Optionally, hydroquinone calcium salt is prepared by the following method: under argon protection, nano calcium carbonate and hydroquinone are heated to 195°C, and after the hydroquinone is melted, the temperature is continued to be raised from 195°C to 215°C, and the heating time is 30 to 60 minutes, and the temperature is maintained at 215°C for 1 hour to obtain hydroquinone calcium salt; the obtained hydroquinone calcium salt is washed with distilled water for 3-6 times, and the ratio of hydroquinone calcium salt to distilled water is 1:5, and then washed with acetone for 3-6 times, and the ratio of hydroquinone calcium salt to acetone is about 1:2, and pure hydroquinone calcium salt is obtained after washing.

[0011] Optionally, the molar ratio of hydroquinone to nano-calcium carbonate is 1:(1-4).

[0012] Optionally, in step 1, the molar ratio of hydroquinone calcium salt, diphenyl sulfone and 4,4'-difluorobenzophenone is 1:(0.5-2):(1-5); and the argon gas flow rate is 2.55 L / min.

[0013] Optionally, in step 2, the ratio of acetone to the crude polyetheretherketone particles is 5:8.

[0014] Optionally, the phosphoric acid-EDTA complex solution is prepared with 35% phosphoric acid, ethylenediaminetetraacetic acid and distilled water.

[0015] Another aspect of the present invention further provides the use of the aforementioned low-VOC polyetheretherketone in medical products, electronic products and electronic cigarettes.

[0016] In another aspect of the present invention, a composite material for preparing an electronic cigarette is provided, comprising 70-90 parts of low-VOC polyetheretherketone, 0-30 parts of filler, and 1-3 parts of color powder.

[0017] Optionally, the filler is one or more of graphite, talc, barium sulfate, calcium sulfate, potassium titanate whisker, calcium carbonate, zirconium dioxide, titanium dioxide, silicon dioxide, magnesium oxide, sodium silicate, tin sulfide, carbon fiber, glass fiber, aluminum oxide, zinc sulfide, and zinc oxide.

[0018] Optionally, the toner is one or more of titanium dioxide, cobalt green, titanium nickel yellow, iron oxide pigment, carbon black, iron manganese black, copper chrome black, iron chrome black, cobalt black, antimony sulfide, ultramarine, and cobalt blue.

[0019] The low-VOC polyetheretherketone of the present invention adds diphenyl sulfone under high temperature conditions when the polyetheretherketone molecular chain is just formed in the polymerization process, that is, when small molecular chains are continuously linked to form large molecular chains and the molecular chains are cross-linked with each other, so as to increase the mobility of the molecular chain and promote the movement of diphenyl sulfone between multiple molecular chains, increase the number of micropores between the polyetheretherketone molecular chains, increase the porosity of the polyetheretherketone, and reduce the residual diphenyl sulfone content of the prepared polyetheretherketone under the same purification conditions, so that the organic gas contained in the polyetheretherketone is fully discharged. The diphenyl sulfone content can be reduced to about 2% as low as detected by the headspace-GC-MS test method, so that the VOC index of the polyetheretherketone meets the requirements of the electronic cigarette field, and can also be used in medical implants, electronic and electrical fields with strict requirements on material purity. DETAILED DESCRIPTION

[0020] The embodiments of the present invention are described in detail below. The embodiments described below are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention. If no specific techniques or conditions are specified in the embodiments, the techniques or conditions described in the literature in this area or the product specifications are used. The reagents or instruments used that do not specify the manufacturer are all conventional products that can be obtained commercially.

[0021] A method for preparing low-VOC polyetheretherketone provided in an embodiment of the present invention comprises the following steps:

[0022] a) using nano-calcium carbonate and molten hydroquinone to react with salt, the molar ratio of hydroquinone to nano-calcium carbonate is 1:1-4, specifically, under the protection of argon, slowly heating from 195°C to 215°C, the heating time is 30-60 minutes, maintaining the temperature at 215°C for 1 hour to obtain hydroquinone calcium salt; washing the obtained hydroquinone calcium salt with distilled water for 3-6 times, the ratio of hydroquinone calcium salt to distilled water is 1:5, and then washing with acetone for 3-6 times, the ratio of hydroquinone calcium salt to acetone is about 1:2, and after washing, pure hydroquinone calcium salt is obtained;

[0023] b) placing hydroquinone calcium salt, diphenyl sulfone and 4,4'-difluorobenzophenone in a molar ratio of 1:(0.5-2):(1-5) in a reaction vessel, and continuously passing high-purity argon gas for protection at a flow rate of 2.55 L / min. After the raw materials are completely melted, starting a stirring paddle for stirring, continuously heating to 280° C., reacting for 1 hour, and then slowly adding diphenyl sulfone. After the newly added diphenyl sulfone is melted, continuing the reaction at 280° C. for 30 minutes, and then quickly pouring the reactants into distilled water and continuously stirring to obtain crude polyetheretherketone particles;

[0024] c) washing with acetone for 4-8 times to remove the solvent diphenyl sulfone, the ratio of acetone to the crude polyetheretherketone being 5:8, then washing with 500 ml of phosphoric acid-ethylenediaminetetraacetic acid composite solution to remove calcium fluoride, and finally washing the crude polyetheretherketone with distilled water for 4-8 times, using 500 ml of distilled water each time, to obtain high-purity polyetheretherketone, the purity of which is not less than 99.99%, and the content of trace metal elements meets the standard of high-purity polyetheretherketone;

[0025] d) Put the polyetheretherketone obtained in step c) into an oven, set the drying temperature to 130-150°C, and volatilize the diphenyl sulfone, fluoroketone, acetone, etc. remaining in the polyetheretherketone into the air, further reducing the remaining substances in the polyetheretherketone, and finally obtaining a low-VOC polyetheretherketone with a VOC content of 2%-10%. The characterization data of VOC is the content of diphenyl sulfone in the gas. The polyetheretherketone of the embodiment of the present invention can contain only about 2% of diphenyl sulfone at the lowest, while the existing conventional PEEK product contains 10% of diphenyl sulfone.

[0026] In the preparation method of the embodiment of the present invention, when the polyetheretherketone molecular chain is just formed in the polymerization process, that is, when the small molecular chains are continuously linked to form large molecular chains and the molecular chains are cross-linked with each other, diphenyl sulfone is added under high temperature conditions to increase the mobility of the molecular chains and promote the movement of diphenyl sulfone between multiple molecular chains, thereby increasing the number of micropores between the polyetheretherketone molecular chains and increasing the porosity of the polyetheretherketone. Under the same purification conditions, the prepared polyetheretherketone has a reduced residual diphenyl sulfone content, so that the organic gas contained in the polyetheretherketone is fully discharged. The headspace-GC-MS test method shows that the diphenyl sulfone content can be reduced to about 2% at the lowest, so that the VOC index of the polyetheretherketone meets the requirements of the electronic cigarette field, and can also be used in medical implants, electronic and electrical fields with strict requirements on material purity.

[0027] The material performance test was carried out using the embodiment of the present invention, and the specific test process included:

[0028] 1. Determination of volatile compound diphenyl sulfone by headspace-gas chromatography-mass spectrometry (GC-MS):

[0029] A. Experimental conditions

[0030] 1. Headspace conditions: headspace temperature 400°C; headspace time 60 min.

[0031] 2. Chromatographic conditions: ECD-5MS column (30m×0.25mm×0.25μm); temperature program: column initial temperature 40℃, hold for 2min, heat to 200℃ at 10℃ / min, hold for 1min, then heat to 400℃ at 25℃ / min; injection port temperature 380℃; carrier gas He; column flow rate 1.0mL / min, constant flow; split ratio 10:1.

[0032] 3. Mass spectrometry conditions: EI ion source, electron energy 70 eV, mass scan range m / z 20-700, quadrupole temperature 350 °C, ion source temperature 400 °C, GC / MS interface temperature 260 °C.

[0033] B. Sample Processing

[0034] 1. Preparation of standard solution: Take 0.05g of standard sample, place it in a 100mL volumetric flask, and dissolve it to 100mL with concentrated sulfuric acid.

[0035] 2. Headspace injection sample preparation: Weigh 2 g of sample, place in a 20 mL headspace bottle, and seal with a cap.

[0036] 2. Viscosity test method

[0037] Viscosity is the ratio of shear stress to shear rate, and its unit is Pa.s.

[0038] The method of measuring the fluidity of plastics by capillary rheometer, also known as the test method of apparent viscosity, is a test method performed using Dynisco laboratory capillary rheometer LCR7001 according to GB / T 25278-2010, ISO 11443, and ASTM D3835 standards. This method allows the plastic melt to be extruded through a capillary die of known size, and the test pressure is tested under the condition of a specified volume flow rate.

[0039] The die of the apparatus used had the following dimensions: 1 mm diameter and 20 mm length, with a die aspect ratio (L / D) of 20.

[0040] Before the measurement, the test samples should be conditioned in accordance with the provisions of GB / T2918-1998, with the conditions being a temperature of 23±2°C, a humidity of 50±10%, and a time of 24±0.5 hours.

[0041] Before testing, ensure that all components reach thermal equilibrium at the test temperature, then start loading, add small amounts of samples to the barrel in batches, and immediately compact with a plunger to prevent air from entering. Load to about 12.5mm from the top of the barrel. Generally, the amount of material used for measurement is 10-15g of polymer, and the loading is completed within 2 minutes.

[0042] The preheating timer started immediately after adding the material. The preheating time was 5 minutes. The test conditions were 400°C and the shear rates were 100s-1, 200s-1, 500s-1, 1000s-1, 2000s-1, 5000s-1 and 10000s-1 respectively.

[0043] 3. Melt index test

[0044] The melt mass flow rate is based on ASTM D1238-04, ISO1133:2005, GB / T3682.1-2018 standards, with the mass extruded in a specified time as the melt mass flow rate, in g / 10min. The SRZ-400E melt flow rate tester from Changchun Intelligent Instrument Equipment Co., Ltd. is used for measurement. The die of the equipment used has the following dimensions: 2.095±0.005mm diameter and 8.000±0.025mm length.

[0045] The material measurement amount is 3-8g polymer. Before the test, the barrel and piston are kept at the test temperature for at least 15 minutes. During the test, the material is loaded within 1 minute. After the loading is completed, preheating begins immediately. The preheating time is 5 minutes. During the preheating, it is necessary to confirm that the temperature returns to the set temperature value. The test is carried out under the test conditions of temperature 380℃ and load 5kg.

[0046] During the test, the length of the cut strips is 10-20mm. All strips with visible bubbles are discarded. After cooling, the remaining strips (3 or more) are weighed one by one to an accuracy of 1mg, and their average mass is calculated and input into the machine for calculation of the melt mass flow rate.

[0047] Furthermore, an embodiment of the present invention also proposes a composite material for preparing an electronic cigarette, which uses the above-mentioned low-VOC polyetheretherketone. Specifically, the composite material includes 70-90 parts of low-VOC polyetheretherketone, 0-30 parts of filler, and 1-3 parts of color powder; wherein the filler is one or more of graphite, talcum powder, barium sulfate, calcium sulfate, potassium titanate whisker, calcium carbonate, zirconium dioxide, titanium dioxide, silicon dioxide, magnesium oxide, sodium silicate, tin sulfide, carbon fiber, glass fiber, aluminum oxide, zinc sulfide, and zinc oxide; the color powder is one or more of titanium dioxide, cobalt green, titanium nickel yellow, iron oxide pigment, carbon black, iron manganese black, copper chrome black, iron chrome black, cobalt black, antimony sulfide, ultramarine, and cobalt blue.

[0048] In order to further explain the technical idea of ​​the present invention, the technical solution of the present invention is now described in conjunction with specific embodiments.

[0049] Example 1

[0050] The hydroquinone calcium salt is prepared by salt-forming reaction of nano-calcium carbonate and molten hydroquinone.

[0051] Take 1101g of hydroquinone and 1000g of nano calcium carbonate (particle size 0.01μm), add them to a three-necked flask and continue to pass high-purity argon protection, the argon flow rate is 2.55L / min. Put the three-necked flask into an electric heating mantle for heating. After the raw materials are completely melted, start the stirring paddle for stirring. At this time, the temperature is about 195℃, heat to 200℃, maintain the temperature for 30min, and then continue to heat up to 215℃. At this time, nano calcium carbonate and hydroquinone react to form salts and release heat. At this time, controlling the reaction temperature is the key. When the temperature reaches 215℃, turn off the heating system immediately, keep stirring, and remove the three-necked flask from the electric heating mantle, put it into the heat transfer oil at 180℃~210℃ for cooling, and maintain the reaction temperature at 215℃. When bubbles no longer appear on the liquid surface in the three-necked flask, the reaction is complete, and the reaction time is about 1 hour. The reactants were poured into 10 L of distilled water and stirred rapidly. After the particles were completely dissolved, they were filtered and recrystallized to obtain hydroquinone calcium salt. The recrystallized product was added to 4000 ml of acetone, stirred until completely dissolved, and filtered again to obtain refined hydroquinone calcium salt.

[0052] Example 2

[0053] Take 1251.6g of diphenyl sulfone, 376g of hydroquinone calcium salt (prepared according to the method of Example 1), and 524g of 4,4'-difluorobenzophenone, add them into a three-necked flask and continue to pass high-purity argon protection, the argon flow rate is 2.55L / min, after the raw materials are completely melted, start the stirring paddle to stir, continue heating to 280°C, react for 1 hour, and then slowly add 1000g of diphenyl sulfone. After the newly added diphenyl sulfone is melted, continue to react at 280°C for 30min, then quickly pour the reactant into distilled water and stir continuously to obtain crude polyetheretherketone particles.

[0054] The crude polyetheretherketone particles were repeatedly washed with acetone for 5 times, using 1000 ml of acetone each time, to remove the solvent diphenyl sulfone, and then 560 ml of 35% phosphoric acid and 116.88 g of ethylenediaminetetraacetic acid were added to 600 ml of distilled water to prepare a phosphoric acid-EDTA complex solution, and the polyetheretherketone was washed once with the phosphoric acid-EDTA complex solution to remove a small amount of calcium fluoride generated by the reaction, and finally washed with distilled water for 5 times, using 1000 ml of distilled water each time, to remove phosphoric acid, and dried to obtain low-VOC polyetheretherketone.

[0055] Example 3

[0056] Take 1251.6g of diphenyl sulfone, 376g of hydroquinone calcium salt (prepared according to the method of Example 1), and 524g of 4,4'-difluorobenzophenone, add them into a three-necked flask and continue to pass high-purity argon protection, the argon flow rate is 2.55L / min, after the raw materials are completely melted, start the stirring paddle to stir, continue heating to 280°C, react for 1 hour, and then slowly add 1500g of diphenyl sulfone. After the newly added diphenyl sulfone is melted, continue to react at 280°C for 30min, then quickly pour the reactant into distilled water and stir continuously to obtain crude polyetheretherketone particles.

[0057] The crude polyetheretherketone particles were repeatedly washed with acetone for 5 times, using 1000 ml of acetone each time, to remove the solvent diphenyl sulfone, and then 560 ml of 35% phosphoric acid and 116.88 g of ethylenediaminetetraacetic acid were added to 600 ml of distilled water to prepare a phosphoric acid-EDTA complex solution, and the polyetheretherketone was washed once with the phosphoric acid-EDTA complex solution to remove a small amount of calcium fluoride generated by the reaction, and finally washed with distilled water for 5 times, using 1000 ml of distilled water each time, to remove phosphoric acid, and dried to obtain low-VOC polyetheretherketone.

[0058] Example 4

[0059] Take 1251.6g of diphenyl sulfone, 376g of hydroquinone calcium salt (prepared according to the method of Example 1), and 524g of 4,4'-difluorobenzophenone, add them into a three-necked flask and continue to pass high-purity argon protection, the argon flow rate is 2.55L / min, after the raw materials are completely melted, start the stirring paddle stirring, continue heating to 280°C, react for 1 hour, and then slowly add 1800g of diphenyl sulfone. After the newly added diphenyl sulfone is melted, continue to react at 280°C for 30min, then quickly pour the reactant into distilled water and stir continuously to obtain crude polyetheretherketone particles.

[0060] The crude polyetheretherketone particles were repeatedly washed with acetone for 5 times, using 1000 ml of acetone each time, to remove the solvent diphenyl sulfone, and then 560 ml of 35% phosphoric acid and 116.88 g of ethylenediaminetetraacetic acid were added to 600 ml of distilled water to prepare a phosphoric acid-EDTA complex solution, and the polyetheretherketone was washed once with the phosphoric acid-EDTA complex solution to remove a small amount of calcium fluoride generated by the reaction, and finally washed with distilled water for 5 times, using 1000 ml of distilled water each time, to remove phosphoric acid, and dried to obtain low-VOC polyetheretherketone.

[0061] Example 5

[0062] Take 1251.6g of diphenyl sulfone, 376g of hydroquinone calcium salt (prepared according to the method of Example 1), and 524g of 4,4'-difluorobenzophenone, add them into a three-necked flask and continue to pass high-purity argon protection, the argon flow rate is 2.55L / min, after the raw materials are completely melted, start the stirring paddle to stir, continue heating to 280°C, react for 1 hour, and then slowly add 2000g of diphenyl sulfone. After the newly added diphenyl sulfone is melted, continue to react at 280°C for 30min, then quickly pour the reactant into distilled water and stir continuously to obtain crude polyetheretherketone particles.

[0063] The crude polyetheretherketone particles were repeatedly washed with acetone for 5 times, using 1000 ml of acetone each time, to remove the solvent diphenyl sulfone, and then 560 ml of 35% phosphoric acid and 116.88 g of ethylenediaminetetraacetic acid were added to 600 ml of distilled water to prepare a phosphoric acid-EDTA complex solution, and the polyetheretherketone was washed once with the phosphoric acid-EDTA complex solution to remove a small amount of calcium fluoride generated by the reaction, and finally washed with distilled water for 5 times, using 1000 ml of distilled water each time, to remove phosphoric acid, and dried to obtain low-VOC polyetheretherketone.

[0064] Example 6

[0065] Take 1251.6g of diphenyl sulfone, 376g of hydroquinone calcium salt (prepared according to the method of Example 1), and 524g of 4,4'-difluorobenzophenone, add them into a three-necked flask and continue to pass high-purity argon protection, the argon flow rate is 2.55L / min, after the raw materials are completely melted, start the stirring paddle to stir, continue heating to 280°C, react for 1 hour, and then slowly add 2200g of diphenyl sulfone. After the newly added diphenyl sulfone is melted, continue to react at 280°C for 30min, then quickly pour the reactant into distilled water and stir continuously to obtain crude polyetheretherketone particles.

[0066] The crude polyetheretherketone particles were repeatedly washed with acetone for 5 times, using 1000 ml of acetone each time, to remove the solvent diphenyl sulfone, and then 560 ml of 35% phosphoric acid and 116.88 g of ethylenediaminetetraacetic acid were added to 600 ml of distilled water to prepare a phosphoric acid-EDTA complex solution, and the polyetheretherketone was washed once with the phosphoric acid-EDTA complex solution to remove a small amount of calcium fluoride generated by the reaction, and finally washed with distilled water for 5 times, using 1000 ml of distilled water each time, to remove phosphoric acid, and dried to obtain low-VOC polyetheretherketone.

[0067] Example 7

[0068] Take 1251.6g of diphenyl sulfone, 376g of hydroquinone calcium salt (prepared according to the method of Example 1), and 524g of 4,4'-difluorobenzophenone, add them into a three-necked flask and continue to pass high-purity argon protection, the argon flow rate is 2.55L / min, after the raw materials are completely melted, start the stirring paddle to stir, continue heating to 280°C, react for 1 hour, and then slowly add 2700g of diphenyl sulfone. After the newly added diphenyl sulfone is melted, continue to react at 280°C for 30min, then quickly pour the reactant into distilled water and stir continuously to obtain crude polyetheretherketone particles.

[0069] The crude polyetheretherketone particles were repeatedly washed with acetone for 5 times, using 1000 ml of acetone each time, to remove the solvent diphenyl sulfone, and then 560 ml of 35% phosphoric acid and 116.88 g of ethylenediaminetetraacetic acid were added to 600 ml of distilled water to prepare a phosphoric acid-EDTA complex solution, and the polyetheretherketone was washed once with the phosphoric acid-EDTA complex solution to remove a small amount of calcium fluoride generated by the reaction, and finally washed with distilled water for 5 times, using 1000 ml of distilled water each time, to remove phosphoric acid, and dried to obtain low-VOC polyetheretherketone.

[0070] Comparative Example 1

[0071] Take 1251.6 g of diphenyl sulfone, 376 g of hydroquinone calcium salt (prepared according to the method of Example 1), and 524 g of 4,4'-difluorobenzophenone, add them into a three-necked flask and continue to pass high-purity argon protection, the argon flow rate is 2.55 L / min, after the raw materials are completely melted, start the stirring paddle, continue to heat to 280 ° C, maintain the temperature for 1 hour, and then quickly pour the reactants into distilled water and stir continuously to obtain polyetheretherketone crude particles.

[0072] The crude polyetheretherketone particles were repeatedly washed with acetone for 5 times, using 1000 ml of acetone each time to remove the solvent diphenyl sulfone, and then 560 ml of 35% phosphoric acid and 116.88 g of ethylenediaminetetraacetic acid were added to 600 ml of distilled water to prepare a phosphoric acid-EDTA complex solution, and the polyetheretherketone was washed once with the phosphoric acid-EDTA complex solution to remove a small amount of calcium fluoride generated by the reaction, and finally washed with distilled water for 5 times, using 1000 ml of distilled water each time to remove phosphoric acid, and dried to obtain polyetheretherketone.

[0073] The low VOC polyetheretherketone prepared in Examples 2-7 and the polyetheretherketone prepared in Comparative Example 1 were subjected to headspace-GC-MS test, melt index test, tensile strength test (using ISO 527-1&2 standard), flexural strength test (using ISO178 standard), and viscosity test, respectively. The test results are shown in Table 1.

[0074] Table 1

[0075]

[0076] It can be found from Table 1 that, compared with conventional polyetheretherketone, low-VOC polyetheretherketone has similar melt index, tensile strength and flexural strength, but slightly lower viscosity. However, in terms of VOC, the diphenyl sulfone content of low-VOC polyetheretherketone is much lower than that of conventional polyetheretherketone. When preparing composite materials for electronic cigarettes in the subsequent preparation, the polyetheretherketone of the above Examples 2-7 can be selected as raw materials.

[0077] Example 8

[0078] Weigh 1500 g of polyetheretherketone prepared in Example 2, 1200 g of zirconium dioxide, 180 g of titanium dioxide, 10 g of cobalt blue and 10 g of carbon black, and add them into a low-speed mixer for mixing at a speed of 200 r / min for 15 min to obtain a mixture; the mixture is extruded and granulated by a twin-screw extruder at an extrusion temperature of 320°C / 350°C / 350°C / 350°C / 350°C / 350°C / 375°C / 375°C, and the cooling method is air cooling to obtain pellets with uniform particles, which are the composite materials for preparing electronic cigarettes.

[0079] Example 9

[0080] Weigh 1500 g of polyetheretherketone prepared in Example 3, 1200 g of zirconium dioxide, 180 g of titanium dioxide, 10 g of cobalt blue and 10 g of carbon black, and add them into a low-speed mixer for mixing at a speed of 200 r / min for 15 min to obtain a mixture; the mixture is extruded and granulated by a twin-screw extruder at an extrusion temperature of 320°C / 350°C / 350°C / 350°C / 350°C / 350°C / 375°C / 375°C, and the cooling method is air cooling to obtain pellets with uniform particles, which are the composite materials for preparing electronic cigarettes.

[0081] Example 10

[0082] Weigh 1500 g of polyetheretherketone prepared in Example 4, 1200 g of zirconium dioxide, 180 g of titanium dioxide, 10 g of cobalt blue and 10 g of carbon black, and add them into a low-speed mixer for mixing at a speed of 200 r / min for 15 min to obtain a mixture; the mixture is extruded and granulated by a twin-screw extruder at an extrusion temperature of 320°C / 350°C / 350°C / 350°C / 350°C / 350°C / 375°C / 375°C, and the cooling method is air cooling to obtain pellets with uniform particles, which are the composite materials for preparing electronic cigarettes.

[0083] Embodiment 11

[0084] Weigh 1500 g of polyetheretherketone prepared in Example 5, 1200 g of zirconium dioxide, 180 g of titanium dioxide, 10 g of cobalt blue, and 10 g of carbon black, and add them into a low-speed mixer for mixing at a speed of 200 r / min for 15 min to obtain a mixture; the mixture is extruded and granulated by a twin-screw extruder at an extrusion temperature of 320°C / 350°C / 350°C / 350°C / 350°C / 350°C / 375°C / 375°C, and the cooling method is air cooling to obtain pellets with uniform particles, which are the composite materials for preparing electronic cigarettes.

[0085] Example 12

[0086] Weigh 1500 g of polyetheretherketone prepared in Example 6, 1200 g of zirconium dioxide, 180 g of titanium dioxide, 10 g of cobalt blue, and 10 g of carbon black, and add them into a low-speed mixer for mixing at a speed of 200 r / min for 15 min to obtain a mixture; the mixture is extruded and granulated by a twin-screw extruder at an extrusion temperature of 320°C / 350°C / 350°C / 350°C / 350°C / 350°C / 375°C / 375°C, and the cooling method is air cooling to obtain pellets with uniform particles, which are the composite materials for preparing electronic cigarettes.

[0087] Example 13

[0088] Weigh 1500 g of polyetheretherketone prepared in Example 7, 1200 g of zirconium dioxide, 180 g of titanium dioxide, 10 g of cobalt blue, and 10 g of carbon black, and add them into a low-speed mixer for mixing at a speed of 200 r / min for 15 min to obtain a mixture; the mixture is extruded and granulated by a twin-screw extruder at an extrusion temperature of 320°C / 350°C / 350°C / 350°C / 350°C / 350°C / 375°C / 375°C, and the cooling method is air cooling to obtain pellets with uniform particles, which are the composite materials for preparing electronic cigarettes.

[0089] Comparative Example 2

[0090] Weigh 1500 g of polyetheretherketone prepared in Comparative Example 1, 1200 g of zirconium dioxide, 180 g of titanium dioxide, 10 g of cobalt blue, and 10 g of carbon black, and add them into a low-speed mixer for mixing at a speed of 200 r / min for 15 min to obtain a mixture; the mixture is extruded and granulated by a twin-screw extruder at an extrusion temperature of 320°C / 350°C / 350°C / 350°C / 350°C / 350°C / 375°C / 375°C, and the cooling method is air cooling to obtain pellets with uniform particles.

[0091] The composite materials prepared in Examples 8-13 and the pellets prepared in Comparative Example 2 were subjected to headspace-GC-MS test, tensile strength test (using ISO 527-1&2 standard), flexural strength test (using ISO 178 standard), melt index test, and viscosity test, respectively, and the test results are shown in Table 2. Melt index and viscosity can reflect lubricity. Under the same melt index conditions, the lower the viscosity value, the better the lubricity of the material.

[0092] Table 2

[0093]

[0094] It can be found from Table 2 that the composites prepared with low-VOC polyetheretherketone have similar melt index, tensile strength and flexural strength, but slightly lower viscosity than those prepared with conventional polyetheretherketone. However, in terms of VOC, the diphenyl sulfone content of low-VOC polyetheretherketone is much lower than that of conventional polyetheretherketone. Melt index and viscosity can reflect lubricity. Under the same melt index conditions, the lower the viscosity value, the better the lubricity of the material, which is more conducive to demolding.

[0095] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0096] Although the embodiments of the present invention have been shown and described above, it is to be understood that the above embodiments are exemplary and are not to be construed as limitations of the present invention. A person skilled in the art may change, modify, replace and vary the above embodiments within the scope of the present invention.

Claims

1. A method for preparing low-VOC polyetheretherketone, It is characterized in that include: Step 1: Under the condition of continuous argon flow, hydroquinone calcium salt, diphenyl sulfone and 4,4'-difluorobenzophenone are heated to melt, stirred with a stirring paddle and continuously heated to 280°C, and diphenyl sulfone is slowly added again after reacting for 60 minutes. After the newly added diphenyl sulfone is melted, the reaction is continued at 280°C for 30 minutes, and the reactant is quickly poured into distilled water and continuously stirred to obtain polyetheretherketone crude particles; Step 2: washing the crude polyetheretherketone particles with acetone for 4-8 times to remove the solvent diphenyl sulfone, then washing with a phosphoric acid-ethylenediaminetetraacetic acid composite solution to remove calcium fluoride, and finally washing the crude polyetheretherketone with distilled water for 4-8 times to obtain low-VOC polyetheretherketone; Among them, the VOC content of low-VOC polyetheretherketone is 2%-10%.

2. The preparation method according to claim 1, It is characterized in that The hydroquinone calcium salt is prepared by the following method: under the protection of argon, nano calcium carbonate and hydroquinone are heated to 195°C, and after the hydroquinone is melted, the temperature is continuously raised from 195°C to 215°C, and the heating time is 30 to 60 minutes; the temperature is maintained at 215°C for 1 hour to obtain the hydroquinone calcium salt; the obtained hydroquinone calcium salt is washed with distilled water for 3 to 6 times, and the ratio of the hydroquinone calcium salt to the distilled water is 1:5; and then washed with acetone for 3 to 6 times, and the ratio of the hydroquinone calcium salt to the acetone is 1:2, and pure hydroquinone calcium salt is obtained after washing.

3. The preparation method according to claim 2, It is characterized in that The molar ratio of hydroquinone to nano-calcium carbonate is 1:(1-4).

4. The preparation method according to claim 1, It is characterized in that In step 1, the molar ratio of hydroquinone calcium salt, diphenyl sulfone and 4,4'-difluorobenzophenone is 1:(0.5-2):(1-5); the argon gas flow rate is 2.55 L / min.

5. The preparation method according to claim 1, It is characterized in that The phosphoric acid-EDTA complex solution is prepared with 35% phosphoric acid, ethylenediaminetetraacetic acid and distilled water.

6. Use of the low-VOC polyetheretherketone prepared by the preparation method according to any one of claims 1 to 5 in non-therapeutic medical products and electronic products.

7. Use of low-VOC polyetheretherketone prepared by the preparation method according to any one of claims 1 to 5 in electronic cigarettes.

8. A composite material for preparing an electronic cigarette, It is characterized in that The invention comprises 70-90 parts of low-VOC polyetheretherketone prepared by the preparation method according to any one of claims 1 to 5, 0-30 parts of filler and 1-3 parts of color powder.

9. The composite material according to claim 8, It is characterized in that The filler is one or more of graphite, talcum powder, barium sulfate, calcium sulfate, potassium titanate whisker, calcium carbonate, zirconium dioxide, titanium dioxide, silicon dioxide, magnesium oxide, sodium silicate, tin sulfide, carbon fiber, glass fiber, aluminum oxide, zinc sulfide, and zinc oxide.

10. The composite material according to claim 8, It is characterized in that The toner is one or more of titanium dioxide, cobalt green, titanium nickel yellow, iron oxide pigment, carbon black, iron manganese black, copper chrome black, iron chrome black, cobalt black, antimony sulfide, ultramarine, and cobalt blue.

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