WO2023040819A1 - 聚醚醚酮及其制备方法 - Google Patents
聚醚醚酮及其制备方法 Download PDFInfo
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- WO2023040819A1 WO2023040819A1 PCT/CN2022/118390 CN2022118390W WO2023040819A1 WO 2023040819 A1 WO2023040819 A1 WO 2023040819A1 CN 2022118390 W CN2022118390 W CN 2022118390W WO 2023040819 A1 WO2023040819 A1 WO 2023040819A1
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- temperature
- hydroquinone
- argon
- preset temperature
- complex
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- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 68
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 222
- 229910052786 argon Inorganic materials 0.000 claims abstract description 114
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 43
- -1 bisphenol compound Chemical class 0.000 claims abstract description 41
- 239000002904 solvent Substances 0.000 claims abstract description 27
- IYRWEQXVUNLMAY-UHFFFAOYSA-N fluoroketone group Chemical group FC(=O)F IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 156
- 239000007789 gas Substances 0.000 claims description 68
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 21
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 20
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 20
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 239000000155 melt Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- ZHUXSAKDWNNBCQ-UHFFFAOYSA-N (3-fluorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC(F)=C1 ZHUXSAKDWNNBCQ-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 229910000018 strontium carbonate Inorganic materials 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims 1
- 150000004053 quinones Chemical class 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 2
- 229960004337 hydroquinone Drugs 0.000 description 75
- 238000006243 chemical reaction Methods 0.000 description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000012153 distilled water Substances 0.000 description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 15
- 239000000843 powder Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000011775 sodium fluoride Substances 0.000 description 11
- 235000013024 sodium fluoride Nutrition 0.000 description 11
- 238000005485 electric heating Methods 0.000 description 8
- 238000009423 ventilation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- LKFIWRPOVFNPKR-UHFFFAOYSA-N (2-fluorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1F LKFIWRPOVFNPKR-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 229920006260 polyaryletherketone Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JAWMENYCRQKKJY-UHFFFAOYSA-N [3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-ylmethyl)-1-oxa-2,8-diazaspiro[4.5]dec-2-en-8-yl]-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]methanone Chemical compound N1N=NC=2CN(CCC=21)CC1=NOC2(C1)CCN(CC2)C(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F JAWMENYCRQKKJY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
Definitions
- the invention relates to the field of polymer materials, in particular to polyether ether ketone and a preparation method thereof.
- Poly(aryl ether ketone) polymer is an aromatic linear polymer material. It is a new type of semi-crystalline aromatic thermoplastic engineering plastic successfully researched and developed in the late 1970s. It has high temperature resistance, chemical resistance, high Strength, high modulus, high fracture toughness and excellent dimensional stability, etc.
- a typical representative of poly(aryl ether ketone) polymers is polyetheretherketone, which has a glass transition temperature (Tg) of 143°C, a melting point of 334°C, and a maximum attainable crystallinity of 48%, generally 20%. ⁇ 30%. Its density in the amorphous state is 1.265g/cm 3 , and the density at the maximum crystallinity is 1.32g/cm 3 .
- the continuous use temperature is 260°C, and the instantaneous use temperature can reach 300°C. It does not decompose in a short time at 400°C. Because of the excellent comprehensive properties of polyether ether ketone, it has a wide range of uses in many fields.
- the synthesis method of polyether ether ketone currently on the market uses diphenyl sulfone as a solvent, and 4,4'-difluorobenzophenone and 1,4-benzenediol undergo nucleophilic copolymerization in the presence of carbonate Preparation, the color of polyetheretherketone prepared by this method is yellow, and it is mainly used in parts and components of various industries, and is widely used.
- the technical problem to be solved by the present invention is how to prepare polyether ether ketone with higher chroma value L and whiter color.
- an object of the present invention is to provide a preparation method of polyether ether ketone.
- the method comprises: feeding argon into a container containing bisphenol compounds to obtain a complex of bisphenol compounds; mixing fluoroketone, alkali metal carbonate, the complex of bisphenol compounds and Solvents are mixed, and the mixture is subjected to temperature programming treatment to generate the polyether ether ketone.
- the bisphenols were protected with argon so that they would not be oxidized to quinones when reacting with fluoroketones and alkali metal carbonates to obtain the color value L Taller, whiter polyether ether ketone solids.
- the complex contains Ar atoms
- forming the complex includes: passing argon gas into a container containing bisphenol compounds, with a flow rate of 20-100ml/min, and heating to make The bisphenol compound is melted; the flow rate of the argon gas is increased to 150-250ml/min, and the bisphenol compound is heated to a first preset temperature and maintained to obtain a complex of the bisphenol compound .
- the bisphenols are protected with argon so that they will not be oxidized to quinones when they react with fluoroketones and alkali metal carbonates, so that the color value can be obtained PEEK solid with higher L* and whiter color.
- the argon gas is introduced under the condition of stirring, and the rotating speed of the stirring is 70-100 rpm. Thereby, the bisphenol compound and the argon gas are fully brought into contact, and the reaction proceeds sufficiently.
- the purity of the argon is 80%-100%.
- the yield of the complex compound of a bisphenol compound can be improved.
- the first preset temperature is 178°C-248°C.
- the bisphenol compound and the argon gas are sufficiently reacted.
- the temperature programming treatment includes: raising the temperature of the mixture of fluoroketone, alkali metal carbonate, bisphenol compound and the solvent to a second preset temperature to obtain The first solution; the first solution is heated to a third preset temperature and maintained to obtain a second solution; the second solution is heated to a fourth preset temperature and maintained to obtain a third solution, wherein , the second preset temperature is 190°C-210°C; the third preset temperature is 270°C-290°C; and the fourth preset temperature is 300°C-320°C.
- the reaction is sufficiently advanced.
- the holding time of the second preset temperature is 60 to 70 minutes; the holding time of the third preset temperature is 50 to 60 minutes; the holding time of the fourth preset temperature is 110-130 minutes.
- the temperature programming treatment is performed under the protection of an inert gas, and before raising the temperature of the mixture to a second preset temperature, further comprising heating the mixture until the mixture melts.
- the reaction is sufficiently advanced.
- the inert gas is argon.
- the bisphenol compound includes at least one of hydroquinone or biquinone, and the purity of the hydroquinone is 90%-103%.
- the occurrence of side reactions can be reduced.
- the purity of the hydroquinone is 98%-102%.
- the occurrence of side reactions can be reduced.
- the fluoroketones include 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 sulfolane, diphenyl sulfone, dimethyl sulfoxide, and methylpyrrolidone
- the molar ratio of the bisphenol compound, the fluoroketone and the alkali metal carbonate is (1-1.2):1:(1-1.1).
- the reaction can be sufficiently advanced.
- the method further includes: separating and purifying the mixed solution containing the polyetheretherketone to obtain the polyetheretherketone solid.
- the purity of polyetheretherketone can be improved by removing other products generated by the reaction.
- the chromaticity value (L*) of the polyether ether ketone is (81.15-88.26).
- white polyether ether ketone was obtained.
- the range of the product of the chromaticity value (L*) and the tensile strength (Rm) of the polyetheretherketone is 9975 ⁇ Rm*L* ⁇ 5100.
- a polyether ether ketone solid is provided.
- the polyether ether ketone solid is prepared by the aforementioned method, so it has all the features and advantages of the polyether ether ketone prepared by the aforementioned method, and will not be repeated here. Generally speaking, at least it has the advantage of higher chromaticity value (L*) and whiter color.
- Fig. 1 shows a schematic flow chart of a method for preparing polyether ether ketone according to an embodiment of the present invention.
- Embodiments of the present invention are described in detail below.
- the embodiments described below are exemplary only for explaining the present invention and should not be construed as limiting the present invention. If no specific technique or condition is indicated in the examples, it shall be carried out according to the technique or condition described in the literature in this field or according to the product specification. The reagents or instruments used were not indicated by the manufacturer, and they were all commercially available conventional products.
- a method for preparing polyether ether ketone comprises: feeding argon gas into a container containing bisphenol compounds to obtain a complex compound of bisphenol compounds; mixing fluoroketone, alkali metal carbonate, complex compounds of bisphenol compounds and a solvent , and the mixture is subjected to a temperature-programmed treatment to generate polyether ether ketone. Therefore, before the preparation of polyetheretherketone, the bisphenols are protected with argon, so that they will not be oxidized when they react with fluoroketones and alkali metal carbonates, so as to obtain a higher color value L* , PEEK solid with white color.
- polyether ether ketone As mentioned earlier, the synthesis method of polyether ether ketone currently on the market is to use diphenyl sulfone as a solvent, and 4,4'-difluorobenzophenone and 1,4-benzenediol are carried out in the presence of sodium carbonate It is prepared by nucleophilic copolymerization reaction.
- the color of polyether ether ketone prepared by this method is yellow. It is mainly used in parts and components in various industries, and is widely used. However, polyetheretherketone with a whiter color is needed in specific fields, and there is no such product on the market, which cannot meet the needs of specific fields.
- the hydroquinone before hydroquinone reacts with 4,4'-difluorobenzophenone and sodium carbonate, the hydroquinone is protected with argon to generate hydroquinone containing Ar atoms
- the complex of hydroquinone will not be oxidized to p-benzoquinone during the subsequent nucleophilic substitution reaction, and the complex of hydroquinone can directly react with sodium carbonate to generate sodium phenate for nucleophilic substitution , the color of polyether ether ketone prepared by this method is white.
- the method may include:
- argon gas is introduced into the container containing the bisphenol compound at a flow rate of 20-100 ml/min, and heated to melt the bisphenol compound.
- the flow rate of argon gas is not particularly limited, and those skilled in the art can freely choose according to needs, specifically, it can be 30, 50, 80 ml/min, etc.
- the flow rate of argon in this step, after heating to melt the bisphenol compound, the flow rate of argon can be increased, and the bisphenol compound can be heated to a first preset temperature and kept there, so as to obtain complexes of bisphenols.
- the flow rate of argon is not particularly limited, and those skilled in the art can freely choose according to needs, for example, it can be 200ml/min to obtain a complex of bisphenol compounds.
- bisphenol compounds can form complexes of bisphenol compounds, specifically, phenolic hydroxyl groups in bisphenol compounds can form weak chemical bonds with Ar atoms.
- the bonding force between the phenolic hydroxyl group and the Ar atom in the complex is weak, and cannot exist stably for a long time at room temperature.
- the complex can continue to form phenate with the alkali metal carbonate in the subsequent process, so as not to affect the subsequent formation of polyether ether ketone.
- the Ar atom in the complex formed in this step has a certain degree of protection for the phenolic hydroxyl group, it can prevent the bisphenol compound from being oxidized to a quinone compound before it forms a phenoxide.
- the bisphenol compound includes at least one of hydroquinone or biquinone, and the purity of hydroquinone is 90%-103%.
- the hydroquinone The purity is 98%-102%.
- the purity of the argon is 80%-100%, preferably, the purity of the argon is 99.0%-99.9%, most preferably 99.999%.
- the yield of the complex compound of a bisphenol compound improves.
- the argon gas can be continuously fed under the condition of stirring, so that the bisphenol compounds can fully form complexes.
- the stirring speed may be 70-100 rpm, specifically 80 rpm.
- the flow rate of the argon gas can also be increased, for example, the flow rate of the argon gas can be increased to 150-250 ml/min, specifically about 200 ml/min.
- the weight of the product after the reaction is greater than the weight of the feed before the reaction, and during the experiment, before the complex is completely generated, the flow rate of the argon gas at the gas outlet of the container is less than that of the argon gas at the gas inlet. gas flow rate. It can be judged that the argon gas passed into the container participated in the reaction, and what this step obtained was not purely molten bisphenols. According to some specific embodiments of the present invention, what is obtained in this step is a hydroquinone complex containing Ar atoms.
- the flow rate and time of argon feeding can be adjusted according to the formation of complexes. Specifically, the reaction between argon and bisphenols is concentrated at the interface, so the flow of argon can be adjusted according to the volume of the container and the area of the interface in this step to ensure that there is a sufficient amount of argon in the container. Gas, can react with bisphenol compounds at the interface in time. After the bisphenol compound is melted, the flow rate of argon can be increased under the condition of stirring to promote the reaction to proceed faster. When it is detected that the flow rate of argon gas at the inlet and outlet of the container is consistent, it can be judged that the reaction is complete, for example, the holding time of the first preset temperature is 1 hour.
- the first preset temperature is 178°C-248°C. Specifically, it may be 188 degrees Celsius, 198 degrees Celsius, 208 degrees Celsius, 218 degrees Celsius, 228 degrees Celsius, 238 degrees Celsius and so on.
- the bisphenol compound and the argon gas are sufficiently reacted.
- the heating rate of the bisphenol compound is not particularly limited, and those skilled in the art can choose according to their needs, as long as they can meet the experimental requirements.
- the fluoroketone, the alkali metal carbonate, the complex compound of the bisphenol compound and the solvent are mixed, and the mixture is subjected to temperature programming treatment.
- the type of fluoroketone is not particularly limited, for example, it may include 4,4'-difluorobenzophenone, 3,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, at least one of benzophenones.
- 4,4'-difluorobenzophenone 3,4'-difluorobenzophenone
- 2,4'-difluorobenzophenone at least one of benzophenones.
- the alkali metal carbonate includes one or two of sodium carbonate, potassium carbonate, strontium carbonate, and cesium carbonate.
- the performance of the polyetheretherketone prepared by the method can be further improved.
- the specific type of solvent is not particularly limited, for example, may include at least one of sulfolane, diphenyl sulfone, dimethyl sulfoxide and methylpyrrolidone.
- sulfolane diphenyl sulfone
- dimethyl sulfoxide dimethyl sulfoxide
- methylpyrrolidone a compound that has a high boiling point inert protic solvent.
- the molar ratio of the bisphenol compound complex, fluoroketone and alkali metal carbonate is (1-1.2):1:(1-1.1), specifically, the molar ratio may be (1 ⁇ 1.2): 1:1.1, 1:1:1.1.
- the inventors have found that when the alkali metal carbonate satisfies the above molar ratio, polyetheretherketone with narrow molecular weight and better mechanical properties can be obtained, and the amount of alkali metal carbonate is not excessive, which is beneficial to the subsequent Product isolation and purification.
- the temperature-programmed treatment includes heating the mixture of fluoroketone, alkali metal carbonate, bisphenol compound complex and solvent to a second preset temperature to obtain a first solution;
- the solution is heated to a third preset temperature and maintained to obtain a second solution;
- the second solution is heated to a fourth preset temperature and maintained to obtain a third solution, wherein the second preset temperature is 190 degrees Celsius to 210 degrees Celsius , and react at a constant temperature for 60 to 70 minutes at the second preset temperature;
- the third preset temperature is 270 degrees Celsius to 290 degrees Celsius, and react at a constant temperature for 50 to 60 minutes at the third preset temperature;
- the fourth preset temperature is 300 Celsius -320 Celsius, and react at a constant temperature for 110 to 130 minutes at the fourth preset temperature, specifically, the second preset temperature is 200 degrees Celsius, and react at a constant temperature for 60 minutes at the second preset temperature;
- the third preset temperature The temperature is 280 degrees Celsius, and the constant temperature reaction is performed at the third prese
- heating through temperature programming can avoid local overheating during the reaction process, improve the uniformity of the reaction, and improve the performance of the polyether ether ketone.
- What needs to be specially explained here is that the heating rate of the mixture when it is heated up to the second preset temperature, from the second preset temperature to the third preset temperature, and from the third preset temperature to the fourth preset temperature is not affected.
- Special restrictions, those skilled in the art can freely choose according to needs, as long as the needs can be met.
- the temperature programming treatment is performed under the protection of an inert gas, and before raising the temperature of the mixture to a second preset temperature, further includes heating the mixture until the mixture melts.
- the reaction is sufficiently advanced.
- the inert gas is preferably argon to further prevent hydroquinone from being oxidized.
- the temperature-programmed treatment is carried out under stirring conditions, for example, the stirring speed may be 60 rpm.
- the third solution was placed in cold distilled water to obtain a white lumpy solid.
- the obtained white blocky solid needs to be further subjected to separation and purification treatment to obtain polyetheretherketone solid. Thereby, other products generated by the reaction can be removed, and the purity of polyetheretherketone can be improved.
- this step after grinding the white blocky solid into powder, wash with ethanol for 5 to 6 times to remove the solvent diphenyl sulfone, and wash with distilled water for 5 to 6 times to remove the sodium fluoride generated by the reaction , to obtain white polyether ether ketone powder.
- the chromaticity value L* of polyetheretherketone is (81.15-88.26).
- white polyether ether ketone was obtained.
- the range of the product of the chromaticity value (L*) and the tensile strength (Rm*) of the polyether ether ketone is 9975 ⁇ Rm*L* ⁇ 5100.
- a polyether ether ketone solid is provided.
- the polyether ether ketone solid is prepared by the aforementioned method, so it has all the features and advantages of the polyether ether ketone prepared by the aforementioned method, and will not be repeated here. Generally speaking, at least it has the advantages of higher chroma value L* and whiter color.
- the sample was injection molded into a chromaticity standard sample under the condition of 380°C, and the chromaticity value L* was tested with a color difference meter.
- the injection molding machine After the injection molding machine is injected into a standard test sample, use the Shimadzu AG-Xplus universal testing machine to test the tensile strength of the sample according to the ISO 527 standard. Form a sample strip with a size of 50 ⁇ 4mm, fix the two ends of the sample on the tensile mold of the universal testing machine, the tensile speed is 2mm/min, and repeat the test for each sample three times to obtain the average value.
- Reduced viscosity is measured in concentrated sulfuric acid (1 wt.%/vol) at 25°C according to ASTM D2857-95 (2007).
- the viscometer tube was a No. 50 Cannon Fenske.
- ground powder approximately average particle size 200-600 ⁇ m was used. The sample was dissolved at room temperature (without heating).
- t solution and t solvent are the efflux times measured for the solution and the blank solvent, respectively. The average of at least 3 measurements was used for the efflux time. Under these conditions, the outflow time should be longer than 200 s and no correction for kinetic energy should be made.
- the purity of hydroquinone in the following examples is all above 99.5%, and the highest purity reaches 99.9%.
- the feeding amount is 300g, and the product weight is greater than 300g, so it can be judged that hydroquinone and argon have generated hydroquinone complexes.
- the hydroquinone in the reactant is the hydroquinone complex containing Ar atom during nucleophilic substitution reaction
- the inert gas of embodiment 1-8 is argon
- the inert gas of Comparative Example 2 was nitrogen. It can be seen from Table 1 that the polyether ether ketone produced in Comparative Example 2 has a lower chromaticity value L*, indicating that the inert gas during the nucleophilic substitution reaction is argon, which can further prevent hydroquinone from being oxidized to a certain extent.
- the polyether ether ketone prepared by the preparation method of the polyetheretherketone of the present invention has a higher chromaticity value L* and a brighter color, and can be applied to specific electronic fields, such as manufacturing wafer carriers, electronic insulating films, and the like.
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Abstract
Description
Claims (15)
- 一种聚醚醚酮的制备方法,其特征在于,包括向含有双酚类化合物的容器内通入氩气,以获得双酚类化合物的络合物;将氟酮、碱金属碳酸盐、所述双酚类化合物的络合物以及溶剂混合,并对混合物进行程序升温处理,以生成所述聚醚醚酮。
- 根据权利要求1所述的方法,其特征在于,所述络合物中含有Ar原子,形成所述络合物包括:向含有双酚类化合物的容器内通入氩气,流量为20-100ml/min,并加热使所述双酚类化合物熔融;提高所述氩气的流量至150-250ml/min,并将所述双酚类化合物加热至第一预设温度并保持,以获得双酚类化合物的络合物。
- 根据权利要求2所述的方法,其特征在于,所述双酚类化合物熔融后,在搅拌的条件下继续通入所述氩气,所述搅拌的转速为70-100rpm。
- 根据权利要求1所述的方法,其特征在于,所述氩气的纯度为80%-100%。
- 根据权利要求2所述的方法,其特征在于,所述第一预设温度为178摄氏度-248摄氏度。
- 根据权利要求1所述的方法,其特征在于,所述程序升温处理包括:将所述氟酮、碱金属碳酸盐、双酚类化合物的络合物以及所述溶剂的混合物升温至第二预设温度,以获得第一溶液;将所述第一溶液升温至第三预设温度并保持,以获得第二溶液;将所述第二溶液升温至第四预设温度并保持,以或得第三溶液;其中,所述第二预设温度为190摄氏度-210摄氏度;所述第三预设温度为270摄氏度-290摄氏度;所述第四预设温度为300摄氏度-320摄氏度。
- 根据权利要求6所述的方法,其特征在于,所述程序升温处理是在惰性气体保护下进行的,将所述混合物升温至第二预设温度之前,进一步包括对所述混合物进行加热至所述混合物熔融。
- 根据权利要求1所述的方法,其特征在于,所述双酚类化合物包括对苯二酚或联苯二酚中的至少一种,所述对苯二酚的纯度为90%-103%。
- 根据权利要求8所述的方法,其特征在于,所述对苯二酚的纯度为98%-102%。
- 根据权利要求1所述的方法,其特征在于,所述的氟酮包括4,4’-二氟二苯甲酮、3,4’-二氟二苯甲酮、2,4’-二氟二苯甲酮中的至少一种;所述碱金属碳酸盐包括碳酸钠、碳酸钾、碳酸锶、碳酸铯中的一种或两种;所述溶剂包括环丁砜、二苯砜、二甲基亚砜和甲基吡咯烷酮中的至少一种;所述双酚类化合物、所述氟酮以及所述碱金属碳酸盐的摩尔比为(1~1.2):1:(1~1.1)。
- 根据权利要求1所述的方法,其特征在于,进一步包括:将含有所述聚醚醚酮的混合溶液进行分离纯化处理,以获得所述的聚醚醚酮固体。
- 根据权利要求1所述的方法,其特征在于,所述聚醚醚酮的色度值(L*)为(81.15-88.26)。
- 根据权利要求1所述的方法,其特征在于,所述聚醚醚酮的色度值(L*)和拉伸强度(Rm*)的乘积范围为9975≥Rm*L*≥5100。
- 根据权利要求7所述的方法,其特征在于,所述惰性气体为氩气。
- 一种聚醚醚酮固体,其特征在于,是由权利要求1-13任一项或权利要求14所述的方法制备的。
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