WO2023016487A1 - 一种高强度、低色度的聚醚醚酮及其制备方法 - Google Patents
一种高强度、低色度的聚醚醚酮及其制备方法 Download PDFInfo
- Publication number
- WO2023016487A1 WO2023016487A1 PCT/CN2022/111423 CN2022111423W WO2023016487A1 WO 2023016487 A1 WO2023016487 A1 WO 2023016487A1 CN 2022111423 W CN2022111423 W CN 2022111423W WO 2023016487 A1 WO2023016487 A1 WO 2023016487A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- preparation
- ether ketone
- polyether ether
- minutes
- polymerizable monomer
- Prior art date
Links
- 239000004696 Poly ether ether ketone Substances 0.000 title claims abstract description 31
- 229920002530 polyetherether ketone Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 230000000269 nucleophilic effect Effects 0.000 claims abstract description 8
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 8
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 6
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 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 28
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 17
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical group C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 7
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 7
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 6
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- -1 diformyl chlorides Chemical class 0.000 claims description 4
- DODIKYQYCCFWRZ-UHFFFAOYSA-N (2-chlorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1Cl DODIKYQYCCFWRZ-UHFFFAOYSA-N 0.000 claims 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 claims description 3
- QSWKFJLPMWWZJE-UHFFFAOYSA-N (4-chlorophenyl)-(2-fluorophenyl)methanone Chemical compound FC1=CC=CC=C1C(=O)C1=CC=C(Cl)C=C1 QSWKFJLPMWWZJE-UHFFFAOYSA-N 0.000 claims description 3
- YGROSAOZMCLHSW-UHFFFAOYSA-N (4-chlorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(Cl)C=C1 YGROSAOZMCLHSW-UHFFFAOYSA-N 0.000 claims description 3
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims description 3
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 claims description 3
- ADUODNZKKNUWBZ-UHFFFAOYSA-N [4-(4-hydroxybenzoyl)phenyl]-(4-hydroxyphenyl)methanone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(C(=O)C=2C=CC(O)=CC=2)C=C1 ADUODNZKKNUWBZ-UHFFFAOYSA-N 0.000 claims description 3
- BSILAEQTGTZMIW-UHFFFAOYSA-N bis(4-phenoxyphenyl)methanone Chemical compound C=1C=C(OC=2C=CC=CC=2)C=CC=1C(=O)C(C=C1)=CC=C1OC1=CC=CC=C1 BSILAEQTGTZMIW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 claims description 3
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 230000035484 reaction time Effects 0.000 abstract description 12
- 229920000642 polymer Polymers 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000001746 injection moulding Methods 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 229920006260 polyaryletherketone Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000008366 benzophenones Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004870 electrical engineering Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
- C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
- C08G65/4093—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group characterised by the process or apparatus used
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/46—Post-polymerisation treatment, e.g. recovery, purification, drying
-
- 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
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
Definitions
- the invention relates to a polyaryletherketone and a preparation method thereof, belonging to the technical field of engineering plastics.
- PEEK polyether ether ketone
- this method usually adopts a kind of bisphenol compound as nucleophilic component and one or more kinds of bishalogenated benzophenones to carry out polycondensation reaction in the presence of alkali metal carbonate in high boiling point inert solvent, usually This type of reaction is carried out under normal pressure and high temperature, the reaction time is relatively long, 5-6 hours, and the final reaction temperature is also 300-400°C. The use of energy and costs in this way is enormous.
- PEEK which is mainly used in wafer carriers and electronic insulating films, often requires PEEK with high strength and brighter color.
- the process for preparing polyetheretherketone required by this requirement is complicated and there are many influencing factors, and no related technology has been found to be disclosed.
- the technical problem to be solved by the invention is how to prepare polyether ether ketone with high strength and low chroma.
- the present invention firstly provides a preparation method of polyether ether ketone, comprising the following steps:
- the first polymerized monomer and the second polymerized monomer undergo a nucleophilic polycondensation reaction in an inert aprotic solvent in the presence of alkali metal carbonate to obtain polyether ether ketone;
- the first polymerizable monomer is hydroquinone, biphenol, 4,4'-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)propane, 1,3-bis- Any one or more of (p-hydroxybenzoyl)benzene, 1,4-bis-(p-hydroxybenzoyl)benzene, ⁇ -naphthol and ⁇ -naphthol;
- the second polymerizable monomer is 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 4-fluoro-4'-chloro-benzophenone, 2-fluoro- 4'-chloro-benzophenone, 2-chloro-4'-fluoro-benzophenone, diphenyl ether, 4,4'-diphenoxybenzophenone, terephthaloyl chloride and isophthalic acid Any one or more of diformyl chlorides.
- the reaction time is shortened, the reaction temperature is lowered, and the energy and cost required for preparation are reduced; at the same time, polyether ether ketone products with high impact strength and brighter color can be prepared .
- 0.15MPa ⁇ 1.0MPa includes any numerical value and all ranges and any sub-ranges therein. For example, including but not limited to 0.2MPa ⁇ 1.0MPa, 0.2MPa ⁇ 0.8MPa, 0.2MPa ⁇ 0.5MPa, 0.5MPa ⁇ 1.0MPa, 0.5MPa ⁇ 0.8MPa, 0.8MPa ⁇ 1.0MPa, 0.15MPa ⁇ 0.8MPa, 0.15MPa ⁇ 0.5MPa, 0.15MPa ⁇ 0.2MPa, 0.15MPa, 0.2MPa, 0.5MPa, 0.8MPa, 1.0MPa.
- the temperature of the nucleophilic polycondensation reaction can be 140°C-260°C, and the time can be 1.5-2.5 hours; the temperature and time include any value, all ranges and any sub-ranges therein. Examples include but are not limited to first reacting at 150-170°C (such as 160°C) for 20-30 minutes (such as 20 minutes, 25 minutes or 30 minutes), and then reacting at 180-210°C (such as 180-200°C, 190°C, React at 200°C or 180°C) for 20-30 minutes (such as 20 minutes, 25 minutes or 30 minutes), and finally react at 225-260°C (such as 225-260°C, 225°C, 240°C, 250°C or 260°C) Until the viscosity of the system reaches 410 Pa.s (such as 55 to 90 minutes, 80 minutes, 90 minutes, 93 minutes, 70 minutes or 55 minutes).
- 150-170°C such as 160°C
- 180-210°C such as 180-200°C, 190°
- the molar ratio of the second polymerizable monomer to the first polymerizable monomer may be (1.0 ⁇ 1.1):1, specifically 1.043:1.
- the alkali metal carbonate can be sodium carbonate and/or potassium carbonate.
- the molar ratio of the alkali metal carbonate to the second polymerizable monomer may be (1.0 ⁇ 1.5):1, specifically 1.0:1.
- the inert aprotic solvent can be at least one of sulfolane, diphenylsulfone, glycerin, dimethylacetamide and methylpyrrolidone.
- the inert atmosphere may specifically be a nitrogen atmosphere.
- the present invention further provides polyether ether ketone prepared by any one of the above-mentioned preparation methods.
- polyetheretherketone of the present invention satisfies the following conditions:
- IS represents the Izod impact strength, the unit is kJm -2 ; L * represents the chromaticity value.
- the polyether ether ketone of the present invention has obvious improvements in mechanical properties and chromaticity.
- the Izod impact strength of the polyether ether ketone may be 5.5-9kJm -2 , such as 5.7kJm -2 , 6.0kJm -2 , 7.3kJm -2 , 8.0kJm -2 or 8.5kJm -2 ;
- the color value L * of polyether ether ketone may be 60-90, such as 80-90.
- the present invention also provides the application of the above-mentioned polyetheretherketone in the preparation of a wafer carrier or an electronic insulating film.
- the QJL impact testing machine is used to detect the Charpy impact strength of the sample according to the ISO179/leA standard, and the ISO180/A standard test
- the Izod impact strength of the sample, the results obtained for the impact strength are CIS and IIS respectively
- the chromaticity of the spline uses a colorimeter, and the chromaticity value of the spline is tested according to the standard of DIN EN ISO 11664-3-2013, and the chromaticity value of the sample is obtained. Chroma value L*.
- the present invention adopts a pressurized method to reduce the reaction temperature and shorten the reaction time, and at the same time accelerates the reaction rate in the positive direction through the chemical reaction kinetics in the pressurized process, so that the alkali metal with low activity
- the carbonate increases the reactivity during the reaction, so that the generated phenoxide can quickly react with the dihalogenated benzophenone, avoiding the long-term residence of the phenoxide to change the color of the product, and the reaction temperature will change after pressurization. If the reaction temperature is too high, the impurity in it will not be cross-linked and discolored, so that the color of the generated polymer will be improved, and the mechanical properties of the generated polymer will be improved.
- a kind of preparation method of polyether ether ketone provided by the invention comprises the following steps:
- the first polymerized monomer and the second polymerized monomer undergo a nucleophilic polycondensation reaction in an inert aprotic solvent in the presence of alkali metal carbonate to obtain polyether ether ketone;
- the first polymerizable monomer is hydroquinone, biphenol, 4,4'-dihydroxybenzophenone, 2,2-bis(4-hydroxyphenyl)propane, 1,3-bis- Any one or more of (p-hydroxybenzoyl)benzene, 1,4-bis-(p-hydroxybenzoyl)benzene, ⁇ -naphthol and ⁇ -naphthol;
- the second polymerizable monomer is 4,4'-difluorobenzophenone, 2,4'-difluorobenzophenone, 4-fluoro-4'-chloro-benzophenone, 2-fluoro- 4'-chloro-benzophenone, 2-chloro-4'-fluoro-benzophenone, diphenyl ether, 4,4'-diphenoxybenzophenone, terephthaloyl chloride and isophthalic acid Any one or more of diformyl chlorides.
- the reaction time is 90 minutes.
- Pour the material into cold distilled water to obtain a white lump crush the white lump with a pulverizer, wash with ethanol for 5 to 6 times to remove the solvent diphenyl sulfone, and wash with distilled water for 5 to 6 times.
- Inorganic salts were generated by 6 removal reactions, and white powder was obtained.
- a standard sample was prepared with a small injection molding machine, and the color value and impact strength were tested. The experimental results are shown in Table 1.
- reaction time is 93 minutes.
- Pour the material into cold distilled water to obtain a white lump crush the white lump with a pulverizer, wash with ethanol for 5 to 6 times to remove the solvent diphenyl sulfone, and wash with distilled water for 5 to 6 times.
- Inorganic salts were generated by 6 removal reactions, and white powder was obtained.
- a standard sample was prepared with a small injection molding machine, and the color value and impact strength were tested. The experimental results are shown in Table 1.
- the preparation method of the polyether ether ketone of the present invention can shorten the reaction time, lower the reaction temperature, and reduce the energy and cost required for preparation; meanwhile, the performance of the polymer is also improved, such as the impact strength of the polymer produced under normal pressure.
- the polymer has been improved, and the color of the polymer is brighter and whiter.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
Description
Claims (10)
- 一种聚醚醚酮的制备方法,包括如下步骤:在惰性气氛中0.15MPa~1.0MPa的压强下,第一聚合单体和第二聚合单体在碱金属碳酸盐存在的条件下于惰性非质子溶剂中经亲核缩聚反应,得到聚醚醚酮;所述第一聚合单体为对苯二酚、联苯二酚、4,4’-二羟基二苯甲酮、2,2-二(4-羟基苯基)丙烷、1,3-双-(对羟基苯甲酰基)苯、1,4-双-(对羟基苯甲酰基)苯、α-萘酚和β-萘酚中的任一种或几种;所述第二聚合单体为4,4’-二氟二苯甲酮、2,4’-二氟二苯甲酮、4-氟-4’-氯-二苯甲酮、2-氟-4’-氯-二苯甲酮、2-氯-4’-氟-二苯甲酮、二苯醚、4,4’-二苯氧基二苯甲酮、对苯二甲酰氯和间苯二甲酰氯中的任一种或几种。
- 根据权利要求1所述的制备方法,其特征在于:所述亲核缩聚反应的温度为140℃~260℃,时间为1.5~2.5小时。
- 根据权利要求1或2所述的制备方法,其特征在于:所述亲核缩聚反应先在150~170℃下反应20~30分钟,然后在180~210℃下反应20~30分钟,最后在225~260下反应55~90分钟。
- 根据权利要求1-3中任一项所述的制备方法,其特征在于:所述第二聚合单体与所述第一聚合单体的摩尔比为(1.0~1.1):1。
- 根据权利要求1-4中任一项所述的制备方法,其特征在于:所述碱金属碳酸盐与所述第二聚合单体的摩尔比为(1.0~1.5):1。
- 根据权利要求1-5中任一项所述的制备方法,其特征在于:所述惰性非质子溶剂为环丁砜、二苯砜、甘油、二甲基乙酰胺和甲基吡咯烷酮中的至少一种。
- 权利要求1-6中任一项所述的制备方法制备得到的聚醚醚酮。
- 根据权利要求7所述的聚醚醚酮,其特征在于:所述聚醚醚酮的性能满足如下条件:IS×L *≥310(1);公式(1)中,IS表示悬臂梁冲击强度,单位为kJm -2;L *表示色度值。
- 根据权利要求8所述的聚醚醚酮,其特征在于:所述聚醚醚酮的悬臂梁冲击强度为5.5~9kJm -2,色度值为60~90。
- 权利要求7-9中任一项所述的聚醚醚酮在制备晶圆承载器或电子绝缘 膜中的应用。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020247004877A KR20240044431A (ko) | 2021-08-13 | 2022-08-10 | 고강도, 저색도 폴리에테르에테르케톤 및 이의 제조 방법 |
EP22855467.1A EP4372028A1 (en) | 2021-08-13 | 2022-08-10 | High-strength and low-chroma polyether ether ketone and preparation method therefor |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110928553.3 | 2021-08-13 | ||
CN202110928553.3A CN113583232B (zh) | 2021-08-13 | 2021-08-13 | 一种高强度、低色度的聚醚醚酮及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2023016487A1 true WO2023016487A1 (zh) | 2023-02-16 |
Family
ID=78257630
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2022/111423 WO2023016487A1 (zh) | 2021-08-13 | 2022-08-10 | 一种高强度、低色度的聚醚醚酮及其制备方法 |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP4372028A1 (zh) |
KR (1) | KR20240044431A (zh) |
CN (1) | CN113583232B (zh) |
WO (1) | WO2023016487A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116120540A (zh) * | 2023-03-28 | 2023-05-16 | 吉林省科众高分子材料股份有限公司 | 一种低温制备聚醚醚酮的方法 |
CN116854904A (zh) * | 2023-08-23 | 2023-10-10 | 安徽卓润新材料科技有限公司 | 一种聚醚醚酮的生产工艺及生产系统 |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113583232B (zh) * | 2021-08-13 | 2022-03-22 | 吉林省中研高分子材料股份有限公司 | 一种高强度、低色度的聚醚醚酮及其制备方法 |
CN113527661B (zh) * | 2021-08-16 | 2022-07-15 | 吉林省中研高分子材料股份有限公司 | 一种聚(芳基醚酮)的制备方法及聚(芳基醚酮) |
CN113583233B (zh) * | 2021-08-16 | 2023-08-04 | 吉林省中研高分子材料股份有限公司 | 采用预混制备聚(芳基醚酮)的方法及聚(芳基醚酮) |
CN114230785B (zh) * | 2021-11-17 | 2023-03-03 | 吉林省中研高分子材料股份有限公司 | 一种耐辐射的聚醚醚酮聚合物及其制备方法 |
CN114920922B (zh) * | 2022-06-27 | 2024-02-06 | 山东君昊高性能聚合物有限公司 | 一种低色度、高拉伸强度聚醚醚酮的制备方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0278720A2 (en) | 1987-02-10 | 1988-08-17 | Victrex Manufacturing Limited | Aromatic polymer |
CN1035679C (zh) | 1992-09-11 | 1997-08-20 | 吉林大学 | 聚芳醚酮-双酚类化合物刚性链有规多嵌段共聚物的制备 |
CN101125923A (zh) | 2006-05-13 | 2008-02-20 | 德古萨有限责任公司 | 聚亚芳基醚酮的制备方法 |
CN101809063A (zh) * | 2007-08-10 | 2010-08-18 | 索维高级聚合物股份有限公司 | 改进的聚(芳基醚酮)类以及生产它们的方法 |
CN104530431A (zh) * | 2014-12-17 | 2015-04-22 | 江门市优巨新材料有限公司 | 一种低色泽和高透光率聚砜树脂的工业化合成方法 |
CN105330839A (zh) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | 一种分子量分布窄的高透光率聚醚砜树脂的高压合成方法 |
CN106167548A (zh) * | 2016-10-20 | 2016-11-30 | 佛山市珀力玛高新材料有限公司 | 高性能聚砜树脂及其合成 |
CN113583232A (zh) * | 2021-08-13 | 2021-11-02 | 吉林省中研高分子材料股份有限公司 | 一种高强度、低色度的聚醚醚酮及其制备方法 |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1974631A (zh) * | 2006-11-21 | 2007-06-06 | 吉林大学 | 聚醚酮酮类高性能热属性聚合物材料的制备方法 |
CN102250299B (zh) * | 2011-06-13 | 2013-03-06 | 马长利 | 封端的聚醚醚酮及其制备方法 |
CN104497239A (zh) * | 2014-12-17 | 2015-04-08 | 江门市优巨新材料有限公司 | 一种低色度、高热稳定性封端的聚醚醚酮树脂的工业化合成方法 |
CN104530418A (zh) * | 2014-12-17 | 2015-04-22 | 江门市优巨新材料有限公司 | 一种高热稳定性封端聚芳醚酮树脂的工业化合成方法 |
CN106188523B (zh) * | 2016-07-20 | 2018-07-13 | 汤原县海瑞特工程塑料有限公司 | 一种制备聚芳醚酮类聚合物的方法 |
CN106750258B (zh) * | 2017-01-24 | 2019-09-03 | 吉林大学 | 薄膜级聚醚醚酮树脂专用料、制备方法及在制备聚醚醚酮/聚醚酰亚胺合金薄膜中的应用 |
WO2019219870A1 (en) * | 2018-05-17 | 2019-11-21 | Solvay Specialty Polymers Usa, Llc | Process for preparing a poly(biphenyl ether sulfone) (ppsu) polymer |
RU2673242C1 (ru) * | 2018-06-27 | 2018-11-23 | Акционерное общество "Институт пластмасс имени Г.С. Петрова" | Способ получения полиэфирэфиркетона |
CN110256643B (zh) * | 2019-06-26 | 2020-03-31 | 南京清研高分子新材料有限公司 | 一种制备聚醚醚酮树脂的方法 |
CN110982062B (zh) * | 2019-12-18 | 2022-04-29 | 山东非金属材料研究所 | 一种低分子量聚醚醚酮的制备方法 |
CN111303406A (zh) * | 2020-02-20 | 2020-06-19 | 青岛新通道合成技术有限公司 | 一种制备聚醚醚酮的方法 |
CN113105620B (zh) * | 2021-04-13 | 2021-12-28 | 吉林大学 | 一种氨基封端的可溶性聚芳醚酮及其制备方法和应用 |
-
2021
- 2021-08-13 CN CN202110928553.3A patent/CN113583232B/zh active Active
-
2022
- 2022-08-10 WO PCT/CN2022/111423 patent/WO2023016487A1/zh active Application Filing
- 2022-08-10 EP EP22855467.1A patent/EP4372028A1/en active Pending
- 2022-08-10 KR KR1020247004877A patent/KR20240044431A/ko unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0278720A2 (en) | 1987-02-10 | 1988-08-17 | Victrex Manufacturing Limited | Aromatic polymer |
CN1035679C (zh) | 1992-09-11 | 1997-08-20 | 吉林大学 | 聚芳醚酮-双酚类化合物刚性链有规多嵌段共聚物的制备 |
CN101125923A (zh) | 2006-05-13 | 2008-02-20 | 德古萨有限责任公司 | 聚亚芳基醚酮的制备方法 |
CN101809063A (zh) * | 2007-08-10 | 2010-08-18 | 索维高级聚合物股份有限公司 | 改进的聚(芳基醚酮)类以及生产它们的方法 |
CN104530431A (zh) * | 2014-12-17 | 2015-04-22 | 江门市优巨新材料有限公司 | 一种低色泽和高透光率聚砜树脂的工业化合成方法 |
CN105330839A (zh) * | 2015-11-30 | 2016-02-17 | 江门市优巨新材料有限公司 | 一种分子量分布窄的高透光率聚醚砜树脂的高压合成方法 |
CN106167548A (zh) * | 2016-10-20 | 2016-11-30 | 佛山市珀力玛高新材料有限公司 | 高性能聚砜树脂及其合成 |
CN113583232A (zh) * | 2021-08-13 | 2021-11-02 | 吉林省中研高分子材料股份有限公司 | 一种高强度、低色度的聚醚醚酮及其制备方法 |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116120540A (zh) * | 2023-03-28 | 2023-05-16 | 吉林省科众高分子材料股份有限公司 | 一种低温制备聚醚醚酮的方法 |
CN116120540B (zh) * | 2023-03-28 | 2024-06-04 | 吉林省科众高分子材料股份有限公司 | 一种低温制备聚醚醚酮的方法 |
CN116854904A (zh) * | 2023-08-23 | 2023-10-10 | 安徽卓润新材料科技有限公司 | 一种聚醚醚酮的生产工艺及生产系统 |
CN116854904B (zh) * | 2023-08-23 | 2024-03-08 | 安徽卓润新材料科技有限公司 | 一种聚醚醚酮的生产工艺及生产系统 |
Also Published As
Publication number | Publication date |
---|---|
CN113583232B (zh) | 2022-03-22 |
EP4372028A1 (en) | 2024-05-22 |
KR20240044431A (ko) | 2024-04-04 |
CN113583232A (zh) | 2021-11-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2023016487A1 (zh) | 一种高强度、低色度的聚醚醚酮及其制备方法 | |
US8236919B2 (en) | Process for preparing a polyether ether ketone | |
EP2773684B1 (en) | Poly(aryl ether sulfone) composition and method of making | |
USH521H (en) | Thermosetting polysulfones | |
EP1272547B1 (en) | Low color poly(biphenyl ether sulfone) and improved process for the preparation thereof | |
EP0106023A2 (en) | End-capped polyarylene polyethers, articles made therefrom and process for preparing such polyarylene polyethers | |
CA2654804C (en) | Polysulphones and polyether sulphones with reduced yellow index and processes for their preparation | |
CN107778486B (zh) | 一种可溶性聚芳醚砜树脂的后处理方法 | |
CN110437437B (zh) | 一种含侧基的高流动性聚芳醚酮三元共聚物的制备方法 | |
CN104479089A (zh) | 一种高热稳定性封端含联苯结构聚芳醚酮树脂的工业化合成方法 | |
CN107936244B (zh) | 一种可溶性聚芳醚酮树脂的后处理方法 | |
CN114891217A (zh) | 一种高性能聚苯砜树脂及其制备方法和应用 | |
CN112795014A (zh) | 一种芳族砜聚合物及其制备方法和应用 | |
JPH0759619B2 (ja) | 高分子量エポキシ樹脂の製造方法 | |
JPH0759620B2 (ja) | 高分子量エポキシ樹脂の製造方法 | |
CN105330841A (zh) | 一种封端改性聚芳醚酮树脂的工业化合成方法 | |
JPH0764911B2 (ja) | 高分子量エポキシ樹脂の製造方法 | |
US8981035B2 (en) | Production method of poly (phenylene ether ether ketone) | |
JPH04120123A (ja) | 高分子量エポキシ樹脂の製造方法 | |
JPH0768327B2 (ja) | 超高分子量エポキシ樹脂の製造方法 | |
CN114015038A (zh) | 聚合物材料及其制备方法、由聚合物材料制备的产品 | |
CN107722203B (zh) | 一种无溶剂制备聚醚醚酮的方法 | |
CN106167548A (zh) | 高性能聚砜树脂及其合成 | |
CN113416306B (zh) | 一种聚芳醚酮树脂及其制备方法 | |
CN110156981B (zh) | 一种聚醚酮聚合物及其制备方法和应用 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22855467 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2024508418 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020247004877 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2022855467 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2022855467 Country of ref document: EP Effective date: 20240213 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |