CN114015038A - Polymer material, preparation method thereof and product prepared from polymer material - Google Patents
Polymer material, preparation method thereof and product prepared from polymer material Download PDFInfo
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- 239000002861 polymer material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000000155 melt Substances 0.000 claims abstract description 18
- 229920006126 semicrystalline polymer Polymers 0.000 claims abstract description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 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 18
- 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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- -1 bisphenol compound Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 238000004519 manufacturing process Methods 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 4
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 4
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000007655 standard test method Methods 0.000 claims description 4
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 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 2
- 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 2
- 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 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- 229950011260 betanaphthol Drugs 0.000 claims description 2
- 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 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- 229920006260 polyaryletherketone Polymers 0.000 abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- 239000004696 Poly ether ether ketone Substances 0.000 description 27
- 229920002530 polyetherether ketone Polymers 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000000605 extraction Methods 0.000 description 12
- 239000012535 impurity Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyethers (AREA)
Abstract
The invention provides a semicrystalline polymer material, a preparation method thereof and a product prepared from the polymer material, wherein the polymer material has a repeating unit of the formula-O-Ph-O-Ph-CO-Ph-, Ph represents a phenylene structure, the balance coefficient eta of the strain release energy rate MFR and the melt mass flow rate G of the polymer material is between [ -0.12,0.12], and the mechanical processability and toughness of the product are balanced, so that the strength, the mechanical processability and the toughness of the product polyaryletherketone product meet the requirements of section bar preparation such as sheet shape, strip shape, tubular shape or plate shape.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a semicrystalline polymer material, a preparation method thereof and a product prepared from the polymer material.
Background
With the continuous advance of society and technology, a large number of thermoplastic polymer materials for industrial use have emerged. However, the demand for materials is increasing and there is a constant demand for materials with improved properties in some respects compared to existing materials. Polyaryletherketone materials among semi-crystalline polymers of the wholly aromatic type are widely used, in particular Polyetheretherketone (PEEK). Because of excellent physical and mechanical properties, thermal properties, electrical properties, high mechanical strength and chemical properties, the composite material has a great deal of applications in the fields of electronic and electrical appliances, mechanical instruments, transportation, aerospace, medical treatment and the like.
For the extrusion of the sheet and the pipe made of the polyaryletherketone material, not only a high-strength polyaryletherketone product is required, but also the mechanical processability and toughness are required, the good mechanical processability can not generate the phenomena of cracking, crushing and the like in the material processing process, and the processability is often represented by the melt mass flow rate; materials characterized by higher fracture toughness, as characterized by strain energy release rates, are more suitable for the manufacture of plates, tubes and parts than materials characterized by lower fracture toughness.
However, the polyaryletherketone products with good mechanical processability tend to have lower toughness, and the polyaryletherketone products with higher fracture toughness tend to have poorer processability.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art.
To this end, in one aspect of the present invention, a semicrystalline polymeric material is provided having a balance of melt mass flow rate and energy strain release rate, the strength, machinability and toughness of the polymeric material being sufficient to meet manufacturing requirements.
A semicrystalline polymeric material having a repeating unit of the formula-O-Ph-CO-Ph-, wherein Ph represents a phenylene structure, and the equilibrium coefficient η of the strain release energy MFR and the melt mass flow rate G of the polymeric material is between [ -0.12,0.12], wherein:
strain Release energy G was measured using the Standard test method ASTM D5045-2014, in J/m2(ii) a v is the rate of temperature rise, in ℃/min; the melt mass flow rate MFR is measured in g/10min using the standard GB/T3682.1-2018 (ISO 1133).
Preferably, the equilibrium coefficient η is between [ -0.08,0.08 ].
Preferably, the polymeric material has a strain energy release rate/melt Mass Flow Rate (MFR). ltoreq.3.0.
In another aspect of the invention, the invention provides a method for preparing a semi-crystalline polymer material, wherein the balance coefficient eta of the strain release energy rate and the melt mass flow rate of the polymer material is between [ -0.12,0.12] by controlling the temperature and the temperature rise rate in the reaction process, and the mechanical processability and toughness of the product are balanced, so that the strength, the mechanical processability and the toughness of the product polyaryletherketone meet the requirements of plate and pipe preparation.
A process for preparing a semicrystalline polymeric material as defined in claim 1 or 2, which comprises:
s1, mixing a bisphenol compound and a double-halogenated organic compound in a solvent diphenyl sulfone under the protection of nitrogen, and adding an alkali carbonate, wherein the molar ratio of the double-halogenated organic compound to the bisphenol compound to the alkali carbonate is 1 (1-1.2) to 1-1.1;
s2, heating the reaction system to 280-310 ℃ at a heating rate of 1-10 ℃/min, and stirring at the temperature to perform the reaction; up to
S3, increasing the viscosity of the reaction system to a desired value, adding an end-capping reagent, and reacting for 15-30min to obtain a product; wherein the molar ratio of the end-capping agent to the dihalogenated organic compound is (0.005-0.015) 1.
Preferably, the heating rate is 2-6 ℃/min.
Preferably, the viscosity of the reaction system is increased to a desired value of 390 to 410Pa · s.
Preferably, the bisphenol compound is one of hydroquinone, biphenol, alpha-naphthol and beta-naphthol, and the double halogenated organic compound is one of 4,4 '-difluorobenzophenone, 4,4' -dichlorobenzophenone, 2,4 '-difluorobenzophenone, 4-fluoro-4' -chlorobenzophenone, 2-chloro-4 '-fluoro-benzophenone, diphenyl ether, 4,4' -diphenoxybenzophenone, terephthaloyl chloride and isophthaloyl chloride.
Preferably, the end-capping agent is 4,4 '-difluorobenzophenone or 4,4' -dichlorobenzophenone.
Preferably, the alkali metal carbonate is sodium carbonate and/or potassium carbonate.
Preferably, the method further comprises a step of purifying the product, wherein the product is extracted by using an organic solvent to remove organic impurities in the product, the organic solvent and inorganic salts in the product are removed by washing with water for multiple times, and finally, the product is dried to obtain the polyether-ether-ketone product.
Preferably, the organic solvent is ethanol or acetone.
Preferably, in the nitrogen protection atmosphere, the bisphenol compound and the double-halogenated organic compound are mixed in the solvent diphenyl sulfone, the temperature is raised to 140-160 ℃ at the temperature raising rate of 1-10 ℃/min, and then the alkali metal carbonate is added.
In yet another aspect of the present invention, the present invention provides a profile, which is a sheet-like, strip-like, tubular or plate-like profile, prepared by melting and extruding a polymer material having a strain-release energy rate MFR and a balance coefficient η of melt mass flow rate G of [ -0.12,0.12 ].
Has the advantages that: the polyaryletherketone products produced by the present invention balance melt mass flow rate and energy strain release rate. The invention balances the machining performance and toughness of the product by controlling the temperature and the heating rate in the reaction process, so that the strength, the machining performance and the toughness of the product polyaryletherketone meet the production requirements of sectional materials such as plates, pipes and the like.
Drawings
FIG. 1 is a graph of strain-release energy rate MFR and melt mass flow rate G of a polymeric material as a function of temperature ramp rate v.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The extrusion of the sections such as plates, pipes and the like made of the polyaryletherketone material requires a polyaryletherketone product with high strength and mechanical processability and toughness, the polyaryletherketone is used as a representative product of the polyaryletherketone, the polyaryletherketone product with good mechanical processability is often lower in toughness, the polyaryletherketone with higher fracture toughness is often poorer in processability, and the mechanical processability of the polyaryletherketone is often represented by melt mass flow rate through research; the toughness is characterized by strain energy release rate, the PEEK with the balance coefficient eta of the strain release energy rate MFR and the melt mass flow rate G between-0.12 and 0.12 meets the requirements on mechanical processability and toughness, and the balance coefficient eta can be controlled between-0.12 and 0.12 by controlling the temperature rising rate of the PEEK generation reaction by further discussing the mechanism.
Discussion of temperature and ramp rate control in the preparation of polyetheretherketone
Example 1
In a three-mouth bottle with a stirrer, one side opening is connected with a three-way pipe for placing a thermometer and a high-purity nitrogen inlet, and the other side opening is connected with a spherical condenser pipe for exhausting. A three-necked flask was placed in an electric jacket, 174.54g (0.8mol) of 4,4' -difluorobenzophenone, 96.89g (0.88mol) of hydroquinone and 800g (3.67mol) of diphenylsulfone were added, the stirring apparatus was started, and high-purity nitrogen gas was introduced at room temperature at a flow rate of 60 ml/min. The reaction was then heated to 150 ℃ at a ramp rate of 2 ℃/min and sodium carbonate 84.79g (0.80mol) was added immediately. The reaction temperature was increased to 300 ℃ at a ramp rate of 2 ℃/min. The temperature of 300 ℃ was maintained until an increase in the viscosity of the reaction mixture to the desired value of 410 pas was observed. Immediately, 1.75g (0.008mol) of 4,4' -difluorobenzophenone was added again to conduct end capping to control the molecular mass of the resulting polymer. After another twenty minutes, the material was poured into cold distilled water to give a lumpy solid.
Grinding the blocks into coarse powder, putting 150g of sample into a fat extractor, adding 500ml of ethanol for extraction for 2h, then pouring out the ethanol, removing organic impurities, adding 500ml of pure water for extraction for 4h to remove the ethanol and inorganic salts, putting the sample into a vacuum drying oven for vacuumizing, heating to 130 ℃ and drying for 10h to obtain a pure polyether ether ketone (PEEK) sample.
The toughness of the polymer product is characterized by the strain energy release rate using standard test method ASTM D5045-2014. The processability of the polymer product is characterized by the melt mass flow rate, the melt Mass Flow Rate (MFR) is tested according to the test standard of GB/T3682.1-2018 (ISO 1133), and the temperature rise rate is adjusted by matching an intelligent temperature controller with a heating sleeve.
Example 2
152.71g (0.7mol) of 4,4' -difluorobenzophenone, 84.77g (0.77mol) of hydroquinone and 752g (3.45mol) of diphenylsulfone were placed in a three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet, the stirring apparatus was started, the three-necked flask was placed in an electric jacket and high-purity nitrogen gas was introduced at room temperature at a flow rate of 60 ml/min. The air was replaced repeatedly, and 74.19g (0.7mol) of sodium carbonate was added immediately after the reaction was heated to 150 ℃ at a heating rate of 4 ℃/min. The reaction temperature was increased to 300 ℃ at a ramp rate of 4 ℃/min. The temperature of 300 ℃ was maintained until an increase in the viscosity of the reaction mixture to the desired value was observed. Immediately, 1.53g (0.007mol) of 4,4' -difluorobenzophenone was added again to conduct end-capping to control the molecular mass of the resulting polymer. After another twenty minutes, the material was poured into cold distilled water to give a lumpy solid.
Grinding the blocks into coarse powder, putting 150g of sample into a fat extractor, adding 500ml of ethanol for extraction for 2h, then pouring out the ethanol, removing organic impurities, adding 500ml of pure water for extraction for 4h to remove the ethanol and inorganic salts, putting the sample into a vacuum drying oven for vacuumizing, heating to 130 ℃ and drying for 10h to obtain a pure polyether ether ketone (PEEK) sample.
Example 3
130.91g (0.6mol) of 4,4' -difluorobenzophenone, 72.66g (0.66mol) of hydroquinone and 700g (3.21mol) of diphenylsulfone were placed in a three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet, the stirring apparatus was started, the three-necked flask was placed in an electric mantle and high-purity nitrogen gas at a flow rate of 60ml/min was introduced at room temperature, air was repeatedly replaced, and 63.59g (0.6mol) of sodium carbonate was immediately added after the reaction was heated to 150 ℃ at a temperature rise rate of 6 ℃/min. The reaction temperature was increased to 300 ℃ at a ramp rate of 6 ℃/min. The temperature of 300 ℃ was maintained until an increase in the viscosity of the reaction mixture to the desired value was observed. Immediately, 1.31g (0.006mol) of 4,4' -difluorobenzophenone was added again to control the molecular mass of the resulting polymer. After another twenty minutes, the material was poured into cold distilled water to give a lumpy solid.
Grinding the blocks into coarse powder, putting 150g of sample into a fat extractor, adding 500ml of ethanol for extraction for 2h, then pouring out the ethanol, removing organic impurities, adding 500ml of pure water for extraction for 4h to remove the ethanol and inorganic salts, putting the sample into a vacuum drying oven for vacuumizing, heating to 130 ℃ and drying for 10h to obtain a pure polyether ether ketone (PEEK) sample.
Example 4
108.09g (0.5mol) of 4,4' -difluorobenzophenone, 60.55g (0.55mol) of hydroquinone and 500g (2.30mol) of diphenylsulfone are placed in a three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet, the stirring device is started, the three-necked flask is placed in an electric heating jacket and high-purity nitrogen gas with the flow rate of 60ml/min is introduced at room temperature, air is repeatedly replaced, and then 53.01 g (0.5mol) of sodium carbonate is added immediately after the reactant is heated to 150 ℃ at the heating rate of 8 ℃/min. The reaction temperature was increased to 300 ℃ at a ramp rate of 8 ℃/min. The temperature of 300 ℃ was maintained until an increase in the viscosity of the reaction mixture to the desired value was observed. Immediately, 1.09g (0.005mol) of 4,4' -difluorobenzophenone was added again to conduct end capping to control the molecular mass of the resulting polymer. After another twenty minutes, the material was poured into cold distilled water to give a lumpy solid.
Grinding the blocks into coarse powder, putting 150g of sample into a fat extractor, adding 500ml of ethanol for extraction for 2h, then pouring out the ethanol, removing organic impurities, adding 500ml of pure water for extraction for 4h to remove the ethanol and inorganic salts, putting the sample into a vacuum drying oven for vacuumizing, heating to 130 ℃ and drying for 10h to obtain a pure polyether ether ketone (PEEK) sample.
Comparative example 1
140.41g (0.65mol) of 4,4' -difluorobenzophenone, 78.72g (0.72mol) of hydroquinone and 700g (3.21mol) of diphenylsulfone were placed in a three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet, the stirring apparatus was started, the three-necked flask was placed in an electric mantle and charged with high-purity nitrogen gas at a flow rate of 60ml/min at room temperature, air was repeatedly replaced, and 68.89g (0.65mol) of sodium carbonate was immediately added after the reaction was heated to 150 ℃ at a temperature rise rate of 1 ℃/min. The reaction temperature was increased to 300 ℃ at a ramp rate of 1 ℃/min. The temperature of 300 ℃ was maintained until an increase in the viscosity of the reaction mixture to the desired value was observed. Immediately, 1.42g (0.0065mol) of 4,4' -difluorobenzophenone was added again to carry out the end capping to control the molecular mass of the resulting polymer. After another twenty minutes, the material was poured into cold distilled water to give a lumpy solid.
Grinding the blocks into coarse powder, putting 150g of sample into a fat extractor, adding 500ml of ethanol for extraction for 2h, then pouring out the ethanol, removing organic impurities, adding 500ml of pure water for extraction for 4h to remove the ethanol and inorganic salts, putting the sample into a vacuum drying oven for vacuumizing, heating to 130 ℃ and drying for 10h to obtain a pure polyether ether ketone (PEEK) sample.
Comparative example 2
117.82g (0.54mol) of 4,4' -difluorobenzophenone, 65.39g (0.60mol) of hydroquinone and 600g (2.75mol) of diphenylsulfone were placed in a three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet, the stirring apparatus was started, the three-necked flask was placed in an electric mantle and charged with high-purity nitrogen gas at a flow rate of 60ml/min at room temperature, air was repeatedly replaced, and 57.23g (0.54mol) of sodium carbonate was immediately added after the reaction was heated to 150 ℃ at a temperature rise rate of 10 ℃/min. The reaction temperature was increased to 300 ℃ at a ramp rate of 10 ℃/min. The temperature of 300 ℃ was maintained until an increase in the viscosity of the reaction mixture to the desired value was observed. Immediately, 1.18g (0.0054mol) of 4,4' -difluorobenzophenone was added again to conduct end-capping to control the molecular mass of the resulting polymer. After another twenty minutes, the material was poured into cold distilled water to give a lumpy solid.
Grinding the blocks into coarse powder, putting 150g of sample into a fat extractor, adding 500ml of ethanol for extraction for 2h, then pouring out the ethanol, removing organic impurities, adding 500ml of pure water for extraction for 4h to remove the ethanol and inorganic salts, putting the sample into a vacuum drying oven for vacuumizing, heating to 130 ℃ and drying for 10h to obtain a pure polyether ether ketone (PEEK) sample.
PEEK Performance characterization of examples 1-4, comparative examples 1-2
The toughness of the polyetheretherketone PEEK prepared in the above examples was characterized by the strain energy release rate, which was tested using the standard test method ASTM D5045-2014. The processability of the polymer products is characterized by the melt mass flow rate, the melt mass flow rate test (MFR) being tested according to the test standard GB/T3682.1-2018 (ISO 1133), the test results being summarized in Table one:
TABLE-Property summary of PEEK of polyetheretherketone
The melt mass flow rate MFR is directly proportional to the reaction temperature rise rate v (v is in the range of 2-6 ℃/min), the energy strain release rate G is inversely proportional to the reaction temperature rise rate v (v is in the range of 2-6 ℃/min), and the relationship between the ratio of the melt mass flow rate MFR to the energy strain release rate G and the temperature rise rate is shown in FIG. 1 in detail according to Table I.
As can be seen by combining the table I and FIG. 1, in examples 1-4 and comparative examples 1 and 2, the invention prepares PEEK under the same test conditions (the effect of the same proportion of the input reaction raw materials on enlarging or reducing can be ignored), and the mutual influence between the melt Mass Flow Rate (MFR) and the strain energy release rate can be balanced by controlling the temperature rise rate to be 2-6 ℃/min, and when the temperature rise rate is controlled to be 2-6 ℃/min, the trend that the reaction energy release rate is reduced along with the increase of MER is reduced, the mechanical processability and toughness of PEEK in the manufacturing process of plates, pipes and parts can be satisfied. When the temperature is between 1 and 2 ℃/min, the reaction energy release rate tends to decrease very rapidly along with the increase of MER, because the polymer generated at a too low temperature raising rate can be separated from the reaction solution and agglomerated to prevent the polymerization reaction from proceeding, the molecular weight of the generated polymer is too low, the strain energy release rate is reduced, and the MFR is increased. When the MER is reduced between 6 and 10 ℃/min, the reaction energy release rate is increased very quickly, and the temperature rise rate is too high, the local temperature in the reactor is too high to accelerate the reaction, and the polymer with higher molecular weight is generated, so that the solution viscosity is too high to continue. Such polymers will have an increased strain energy release rate, but a reduced MFR. The strain energy release rate decreases with increasing melt Mass Flow Rate (MFR) because the melt Mass Flow Rate (MFR) decreases with increasing melt viscosity and the strain energy release rate increases.
It can be seen that the prepared PEEK has the property of strain energy release rate/melt Mass Flow Rate (MFR) of 3.0 or less. But not enough to reveal the equilibrium relationship of the rate of temperature rise with the strain energy release rate/melt mass flow rate.
To balance the relationship between the melt mass flow rate MFR and the energy strain release rate G, the equilibrium is made by controlling the rate of temperature rise v of the reaction, thereby introducing the following formula (1):
wherein the temperature rise rate interval is [ v ]1,v2]MFR is the melt mass flow rate in g/10 min; g is the energy strain release rate in J/m2And v is the rate of temperature rise in ℃/min.
According to the test data in the first table, the equilibrium coefficient is calculated according to the formula (1) and summarized in the second table:
table two balance coefficient summary table
| Speed of temperature riseInterval of rate | 1-2 | 2-4 | 4-6 | 6-8 | 8-10 |
| Coefficient of equilibrium eta | 1.003 | 0.072 | 0.044 | -0.175 | -0.310 |
Referring to the attached figure 1, the equilibrium coefficient is between-0.12 and 0.12, the heating rate is controlled between 2 and 6 ℃/min, and the equilibrium melt Mass Flow Rate (MFR) and the strain energy release rate are balanced, so that the mechanical processability and toughness of PEEK in the manufacturing process of plates, pipes and parts can be met.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (11)
1. A semicrystalline polymeric material characterized in that said polymeric material has a repeating unit of the formula
-O-Ph-O-Ph-CO-Ph-
Wherein Ph represents a phenylene structure, and
the equilibrium coefficient η of the strain-release energy rate MFR and the melt mass flow rate G of the polymeric material is between [ -0.12,0.12], wherein:
wherein the strain release energy rate G is tested by adopting a standard test method ASTM D5045-2014, and the unit is J/m2(ii) a v is the rate of temperature rise, in ℃/min; the melt mass flow rate MFR is measured in g/10min using the standard GB/T3682.1-2018 (ISO 1133).
2. The semi-crystalline polymeric material of claim 1, wherein the equilibrium coefficient η is between [ -0.08,0.08 ].
3. A method for preparing a semicrystalline polymeric material as defined in claim 1 or 2, characterized in that:
s1, mixing a bisphenol compound and a double-halogenated organic compound in a solvent diphenyl sulfone under the protection of nitrogen, and adding an alkali carbonate, wherein the molar ratio of the double-halogenated organic compound to the bisphenol compound to the alkali carbonate is 1 (1-1.2) to 1-1.1;
s2, heating the reaction system to 280-310 ℃ at a heating rate of 1-10 ℃/min, and stirring at the temperature to perform the reaction; up to
S3, increasing the viscosity of the reaction system to a desired value, adding an end-capping reagent, and reacting for 15-30min to obtain a product; wherein the molar ratio of the end-capping agent to the dihalogenated organic compound is (0.005-0.015) 1.
4. The method of preparing a semi-crystalline polymer material according to claim 3, wherein the temperature increase rate is 2 to 6 ℃/min.
5. The method for producing a semicrystalline polymer material according to claim 3, characterized in that the viscosity of the reaction system is increased to a desired value of 390 to 410 Pa-s.
6. The method of claim 3, wherein the bisphenol compound is one of hydroquinone, biphenol, alpha-naphthol, and beta-naphthol, and the bis-halogenated organic compound is one of 4,4 '-difluorobenzophenone, 4,4' -dichlorobenzophenone, 2,4 '-difluorobenzophenone, 4-fluoro-4' -chlorobenzophenone, 2-chloro-4 '-fluorobenzophenone, diphenyl ether, 4,4' -diphenoxybenzophenone, terephthaloyl chloride, and isophthaloyl chloride.
7. The method of preparing a semicrystalline polymeric material as defined in any one of claims 4 to 6 wherein the end-capping agent is 4,4 '-difluorobenzophenone or 4,4' -dichlorobenzophenone.
8. The method for preparing a semicrystalline polymeric material as defined in claim 7, characterized in that the alkali metal carbonate is sodium carbonate and/or potassium carbonate.
9. A profile, characterized by being made of a semicrystalline polymer material according to any one of claims 1 to 8 by melt extrusion.
10. A sheet prepared from the semicrystalline polymer material according to any one of claims 1 to 8.
11. A pipe produced from the semicrystalline polymer material according to any one of claims 1 to 8.
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| US20160152769A1 (en) * | 2013-06-26 | 2016-06-02 | Victrex Manufacturing Limited | Polymeric materials |
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| EP3783047A1 (en) * | 2019-08-20 | 2021-02-24 | Solvay Specialty Polymers USA, LLC. | Peek-peodek copolymer and method of making the copolymer |
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| JP2011093965A (en) * | 2009-10-27 | 2011-05-12 | Kaneka Corp | Method for producing polyethers |
| US20160152769A1 (en) * | 2013-06-26 | 2016-06-02 | Victrex Manufacturing Limited | Polymeric materials |
| US20200024393A1 (en) * | 2016-09-26 | 2020-01-23 | Victrex Manufacturing Limited | Polymers and process for their manufacture |
| EP3783047A1 (en) * | 2019-08-20 | 2021-02-24 | Solvay Specialty Polymers USA, LLC. | Peek-peodek copolymer and method of making the copolymer |
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| CN114230785A (en) * | 2021-11-17 | 2022-03-25 | 吉林省中研高分子材料股份有限公司 | Radiation-resistant polyether-ether-ketone polymer and preparation method thereof |
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