CN117343327A - Low-volatile crosslinked polyphenylene sulfide and preparation method thereof - Google Patents
Low-volatile crosslinked polyphenylene sulfide and preparation method thereof Download PDFInfo
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 90
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 67
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 40
- 239000011593 sulfur Substances 0.000 claims abstract description 40
- 239000012043 crude product Substances 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 230000018044 dehydration Effects 0.000 claims abstract description 17
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 17
- 238000007599 discharging Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 22
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 239000001301 oxygen Substances 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 230000006837 decompression Effects 0.000 claims description 13
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 150000003857 carboxamides Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 32
- 239000002245 particle Substances 0.000 abstract description 17
- 238000001704 evaporation Methods 0.000 abstract description 14
- 230000008020 evaporation Effects 0.000 abstract description 14
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000012535 impurity Substances 0.000 description 8
- 230000009286 beneficial effect Effects 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005303 weighing Methods 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
-
- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0277—Post-polymerisation treatment
- C08G75/0281—Recovery or purification
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention provides a low-volatile crosslinked polyphenylene sulfide and a preparation method thereof, and particularly relates to the technical field of high polymer materials. The preparation method comprises the following steps: A. mixing a sulfur source, an alkali solution and a solvent, heating for dehydration, and adding a dihalogen aromatic compound and the solvent for polymerization reaction after dehydration; B. discharging after the polymerization reaction is finished, and enabling the materials to enter a dryer after being circulated in a discharging pipeline for multiple times of heating and temperature rising-pressure reducing, and continuously drying to obtain a polyphenylene sulfide crude product; C. washing and purifying the polyphenylene sulfide crude product for multiple times to obtain the linear polyphenylene sulfide; D. the linear polyphenylene sulfide is subjected to heat treatment to obtain the low-volatile crosslinked polyphenylene sulfide. According to the preparation method, through three-step reduced pressure flash evaporation, the particle size of the crude product particles is reduced, and the porosity of the crude product is improved, so that volatile components in the product are more effectively and fully removed in the subsequent flash evaporation, drying and heat treatment or thermal oxidation processes.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a low-volatile crosslinked polyphenylene sulfide and a preparation method thereof.
Background
Polyphenylene sulfide is called polyphenylene sulfide, PPS for short, is thermoplastic resin with phenylthio in the main chain, and is a crystalline polymer. High melt flowability is required for molding and injection molding of polyphenylene sulfide products of complex shapes, but PPS having high melt flowability generally contains a large amount of low molecular weight components and a larger number of terminal groups, and the amount of volatile components is large during melting, which causes a large amount of mold scales and tends to block the mold vent. The fiber-grade PPS needs low melt fluidity, and a high volatile content causes yarn breakage during spinning, which seriously affects the stability of production, so that low volatile PPS is highly desired.
For PPS produced by the flash process, it is inevitable to contain a large amount of low molecular weight components, and the problem of high volatile content is more remarkable. Volatile matters can be reduced to a certain extent through heat treatment or thermal oxidation treatment, but the melt fluidity of the product can be synchronously reduced during the heat treatment, so that the crosslinked polyphenylene sulfide is prepared, and the problems of low fluidity and high gel content of the product can be caused by too long treatment time.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of low-volatile crosslinked polyphenylene sulfide, which aims to further remove volatile components in linear polyphenylene sulfide and simultaneously improve the technical problem of low volatile removal efficiency in heat treatment.
The second object of the present invention is to provide a low-volatile crosslinked polyphenylene sulfide.
In order to solve the technical problems, the invention adopts the following technical scheme:
the first aspect of the invention provides a preparation method of low-volatile crosslinked polyphenylene sulfide, which comprises the following steps:
A. mixing a sulfur source, an alkali solution and a solvent, heating for dehydration, and adding a dihalogen aromatic compound and the solvent for polymerization reaction after dehydration;
B. after the polymerization reaction is finished, directly discharging without cooling, and enabling the materials to enter a dryer after being subjected to multiple heating temperature rise-decompression cycles in a discharging pipeline, and continuously drying to obtain a polyphenylene sulfide crude product;
C. washing and purifying the polyphenylene sulfide crude product to obtain the linear polyphenylene sulfide;
D. the linear polyphenylene sulfide is subjected to heat treatment or thermal oxygen treatment to reduce volatile matters so as to obtain the low-volatile crosslinked polyphenylene sulfide.
Further, in the step B, the number of heating temperature rise-decompression cycles is not less than 2.
Preferably, the number of the heating temperature rise-decompression cycles is 3, specifically: and heating the reactant by a first heater, then performing first decompression, continuing to heat by a second heater, then performing second decompression, finally performing third decompression after heating by a third heater, and feeding the reactant subjected to multiphase mixing into a dryer, and continuously drying to obtain a polyphenylene sulfide crude product.
Further, the temperature after the first heating temperature and the second heating temperature are respectively 270 ℃ to 290 ℃.
Preferably, the pressure after the first depressurization is 0.7MPa to 0.9MPa.
Preferably, the pressure after the second depressurization is 0.45MPa to 0.6MPa.
Preferably, the pressure after the third pressure reduction is normal pressure.
Further, the third heating temperature rise is performed by mixing with a high temperature non-reactive gas.
Preferably, the temperature of the high temperature non-reactive gas is 280 ℃ to 320 ℃.
Preferably, the high temperature non-reactive gas is used in an amount of 25% to 100% by mass of the reaction mixture.
Preferably, the high temperature non-reactive gas is nitrogen or water vapor.
Further, the temperature of the drying is 240-260 ℃, and the drying is carried out until the temperature of the materials reaches more than 240 ℃.
Further, in the step D, the heat treatment or the thermal oxygen treatment process is performed under the protection of inert gas.
Preferably, the temperature of the heat treatment is 200 ℃ to 240 ℃.
Preferably, the temperature of the thermal oxygen treatment is 200-240 ℃, and the volume content of oxygen is 2-10%.
Preferably, in step a, the temperature of the polymerization reaction is 240 ℃ to 270 ℃.
Further, in the step A, the temperature is raised and the dehydration is carried out to obtain dehydration liquid, and the H in the dehydration liquid is calculated by 1mol of sulfur source 2 The molar ratio of O to sulfur source is 1.0-1.5.
Preferably, in step A, after the dihaloaromatic compound and the solvent are added, the molar ratio of the reaction solvent to the sulfur source is 3.0 to 4.0, based on 1mol of the sulfur source, before the polymerization reaction.
Preferably, in step A, the molar ratio of base to sulfur source is from 0.96 to 1.00, based on 1mol of sulfur source.
Preferably, the molar ratio of dihaloaromatic compound to sulfur source is from 1.04 to 1.10, based on 1mol of sulfur source.
Further, the sulfur source comprises a sulfur hydride.
Preferably, the alkali solution comprises a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, in the alkali solution, the mass fraction of alkali is 30% -50%.
Preferably, the solvent comprises an organic amide.
Preferably, the organic amide comprises N-methylpyrrolidone.
Preferably, the dihaloaromatic compound comprises p-dichlorobenzene.
Further, in the step C, the water washing comprises normal pressure water washing and high temperature water washing.
Preferably, the high temperature water washing temperature is 180-220 ℃.
Preferably, the pH of the slurry mixture of the crude product and water before high temperature washing is 4.5-5.5.
The second aspect of the invention provides the low-volatile crosslinked polyphenylene sulfide prepared by the preparation method.
Further, the linear polyphenylene sulfide has an MFR value of 2000 to 7000, preferably 3000 to 6000;
preferably, the ash content of the linear polyphenylene sulfide is < 0.25wt.%;
preferably, the content of volatile components in the linear polyphenylene sulfide is < 0.7wt.%.
Further, the low-volatile crosslinked polyphenylene sulfide has an MFR value of 100 to 1000, preferably 100 to 500;
preferably, the ash content of the low volatile crosslinked polyphenylene sulfide is < 0.25wt.%, preferably < 0.15wt.%;
preferably, the content of volatile components in the low-volatile crosslinked polyphenylene sulfide is < 0.4wt.%, preferably < 0.2wt.%.
Compared with the prior art, the invention has at least the following beneficial effects:
according to the preparation method of the low-volatile crosslinked polyphenylene sulfide, provided by the invention, the particle size of the crude product particles is reduced through three-step temperature rise and pressure reduction flash evaporation, and the porosity of the crude product is improved, so that the volatile components in the product are more effectively and fully removed in the subsequent flash evaporation, drying and thermal oxidation treatment processes. The reduction of the particle size and the improvement of the porosity of the product are beneficial to the removal of micromolecular impurities and ash in the subsequent washing and purifying process, and the volatile matters and the ash of the product are further reduced, so that the high-quality product is prepared.
The ash content of the low-volatile crosslinked polyphenylene sulfide provided by the invention is as low as below 0.25wt.%, and the volatile content of the low-volatile crosslinked polyphenylene sulfide is lower than 0.40wt.%, so that a raw material with better performance is provided for molding injection molding, the use scene of the low-volatile crosslinked polyphenylene sulfide is widened, and the development of downstream industry is promoted.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of embodiments of the present invention may be arranged and designed in a wide variety of different configurations.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The low volatile component in the "low volatile crosslinked polyphenylene sulfide" of the present invention means a low volatile component.
The first aspect of the invention provides a preparation method of crosslinked polyphenylene sulfide, which comprises the following steps:
A. mixing a sulfur source, an alkali solution and a solvent, heating for dehydration, and adding a dihalogen aromatic compound and the solvent for polymerization reaction after dehydration;
B. after the polymerization reaction is finished, directly discharging without cooling, and enabling the materials to enter a dryer after being subjected to multiple heating temperature rise-decompression cycles in a discharging pipeline, and continuously drying to obtain a polyphenylene sulfide crude product;
C. washing and purifying the polyphenylene sulfide crude product to obtain the linear polyphenylene sulfide;
D. the linear polyphenylene sulfide is subjected to heat treatment or thermal oxygen treatment to reduce volatile components.
According to the preparation method of the low-volatile crosslinked polyphenylene sulfide, provided by the invention, the particle size of the crude product particles is reduced through three-step temperature rise and pressure reduction flash evaporation, and the porosity of the crude product is improved, so that the volatile components in the product are more effectively and fully removed in the subsequent flash evaporation, drying and thermal oxidation treatment processes. The reduction of the particle size and the improvement of the porosity of the product are beneficial to the removal of micromolecular impurities and ash in the subsequent washing and purifying process, and the volatile matters and the ash of the product are further reduced, so that the high-quality product is prepared.
The principle of the invention is that the reaction solvent and the low-boiling impurities are partially vaporized by gradually decompressing and flashing, and the heat exchange is carried out for many times to supplement the heat of the high-temperature materials, and then the high-temperature gases supplemented by mixing are carried out for the last step of flashing, so that the atomization effect and the solidification speed in the final flashing are greatly improved, more volatile matters are removed, and meanwhile, the generated crude product particles are smaller, the porosity and the specific surface area are higher, thereby being beneficial to the removal of volatile impurities and ash in the subsequent drying, water washing and heat treatment processes.
Further, in the step B, the number of heating temperature rise-decompression cycles is not less than 2.
Preferably, the number of heating up-depressurizing cycles is 3, specifically: and after the first heating and the temperature rising, performing first decompression, continuing the second heating and the temperature rising, performing second decompression, and finally, after the third heating and the temperature rising, performing third decompression to obtain a polyphenylene sulfide crude product.
In some embodiments of the invention, the third depressurization is performed directly in an atmospheric dryer to avoid clogging of the piping by solidified particles after flash evaporation.
Further, the temperature after the first heating temperature and the second heating temperature are respectively 270 ℃ to 290 ℃. At this temperature, the reaction mixture is still stable, and excessive temperatures may lead to decomposition of the reaction mixture.
In some embodiments of the invention, the temperature after the first heating and the second heating is typically, but not limited to 270 ℃, 275 ℃,280 ℃, 285 ℃, or 290 ℃.
Preferably, the pressure after the first depressurization is 0.7MPa to 0.9MPa.
Preferably, the pressure after the second depressurization is 0.45MPa to 0.6MPa.
The pressure gradient after multiple times of decompression is reduced, and the amplitude of each time of decompression cannot be too large, so that excessive flash evaporation is avoided, the temperature of a reaction mixture is too low, polyphenylene sulfide particles are separated out, and a pipeline is blocked. In some embodiments of the present invention, the pressure after the first depressurization is typically, but not limited to, 0.7MPa, 0.75MPa, 0.8MPa, 0.85MPa, or 0.9MPa; the pressure after the second depressurization is typically, but not limited to, 0.5MPa, 0.52MPa, 0.54MPa, 0.56MPa, 0.58MPa or 0.6MPa.
Preferably, the pressure after the third pressure reduction is normal pressure, so that the solvent and the low-boiling impurities are vaporized as much as possible for complete flash evaporation.
Further, the third heating temperature rise is performed by mixing with a high-temperature gas. The mixed high-temperature gas can improve the atomizing effect, can provide additional heat and is easy to adjust.
Preferably, the high temperature gas is nitrogen or steam at a temperature of 280 ℃ to 320 ℃.
Preferably, the usage amount of the high-temperature gas is 25% -100% of the mass of the reaction liquid. Within this ratio range, the reaction solution can be sufficiently atomized and dried without wasting heat, typically but not limitatively, the superheated steam is used in an amount of 25%, 40%, 60%, 80%, 100% of the mass of the reaction solution.
Further, in the step A, the temperature is raised and the dehydration is carried out to obtain dehydration liquid, and the H in the dehydration liquid is calculated by 1mol of sulfur source 2 The molar ratio of O to sulfur source is 1.0-1.5.
Preferably, in step A, after the dihaloaromatic compound and the solvent are added, the molar ratio of the reaction solvent to the sulfur source is 3.0 to 4.0, based on 1mol of the sulfur source, before the polymerization reaction.
When the molar ratio of the reaction solvent to the sulfur source is lower than 3.0, the viscosity of the reaction solution is higher, the atomization effect during flash evaporation is poor, and the product particles are large; when the molar ratio of the reaction solvent to the sulfur source is higher than 4.0, the solvent amount is too large, the solvent cannot be fully volatilized, particles are coalesced in the drying process, and the product particles are large. Typically, but not by way of limitation, the molar ratio of reaction solvent to sulfur source is 3.0, 3.3, 3.7 or 3.9.
Further, in the step A, the molar ratio of the base to the sulfur source is 0.96 to 1.00 based on 1mol of the sulfur source.
Preferably, the molar ratio of dihaloaromatic compound to sulfur source is from 1.04 to 1.10, based on 1mol of sulfur source.
When the molar ratio of the dihalogen aromatic compound to the sulfur source is lower than 1.04, the fluidity of the product is low, the viscosity of the reactant is high, the atomization effect during flash evaporation is poor, and the product particles are large; when the molar ratio of the dihalogenated aromatic compound to the sulfur source is higher than 1.10, the product has high fluidity and poor performance, and cannot meet the downstream application requirements. Typically, but not by way of limitation, the molar ratio of dihaloaromatic compound to sulfur source is 1.04, 1.06, 1.08.
Further, the sulfur source includes a sulfur hydride, such as sodium hydrosulfide.
Preferably, the alkali solution comprises a sodium hydroxide solution or a potassium hydroxide solution.
Preferably, in the alkali solution, the mass fraction of alkali is 30% -50%.
Preferably, the solvent comprises an organic amide.
Preferably, the organic amide comprises N-methylpyrrolidone.
Preferably, the dihaloaromatic compound comprises p-dichlorobenzene.
Further, in the step A, the temperature of the polymerization reaction is 240 ℃ to 270 ℃.
Preferably, in the step C, the temperature of the drying is 240-260 ℃ and the material is dried to a temperature above 240 ℃.
Further, in the step C, the water washing comprises normal pressure water washing and high temperature water washing.
Preferably, the high temperature water wash is at a temperature of 180 ℃ to 220 ℃ and is beneficial to the removal of volatile impurities and ash.
Preferably, the pH of the slurry mixture of the crude product and water before high temperature washing is 4.5-5.5.
Further, in the step D, the heat treatment or the thermal oxygen treatment process is performed under the protection of inert gas.
The heat treatment or the thermal oxygen treatment at a higher temperature can further remove volatile substances in the product, but the fluidity of the product is inevitably reduced continuously and the product is converted into crosslinked polyphenylene sulfide.
Preferably, the temperature of the heat treatment is 200 ℃ to 240 ℃. Typically, but not by way of limitation, the temperature of the heat treatment is 200 ℃, 210 ℃, 220 ℃, 230 ℃, or 240 ℃.
Preferably, the temperature of the thermal oxygen treatment is 200-240 ℃, and the volume content of oxygen is 2-10%. The volume content of oxygen affects the rate of decrease in product flowability during the thermal oxygen treatment.
Typically, but not by way of limitation, the temperature of the thermal oxygen treatment is 200 ℃, 210 ℃, 220 ℃, 230 ℃, or 240 ℃; the volume content of oxygen is 2%, 4%, 6%, 8% or 10%.
The second aspect of the invention provides the low-volatile crosslinked polyphenylene sulfide prepared by the preparation method.
The low-volatile crosslinked polyphenylene sulfide provided by the invention has the advantages that the content of volatile components is as low as below 0.4wt.%, the ash content is as low as below 0.25wt.%, the raw materials with better performance are provided for molding injection molding, the use scene of the crosslinked polyphenylene sulfide is widened, and the development of downstream industries is promoted.
Further, the linear polyphenylene sulfide has an MFR value of 2000 to 7000, preferably 3000 to 6000;
preferably, the ash content of the linear polyphenylene sulfide is < 0.25wt.%;
preferably, the content of volatile components in the linear polyphenylene sulfide is < 0.7wt.%.
Further, the low-volatile crosslinked polyphenylene sulfide has an MFR value of 100 to 1000, preferably 100 to 500;
preferably, the ash content of the low volatile crosslinked polyphenylene sulfide is < 0.25wt.%, preferably < 0.15wt.%;
preferably, the content of volatile components in the low-volatile crosslinked polyphenylene sulfide is < 0.40wt.%, preferably < 0.20wt.%.
Some embodiments of the present invention will be described in detail below with reference to examples. The following embodiments and features of the embodiments may be combined with each other without conflict. The raw material purchase in the following examples and comparative examples was obtained by commercial purchase unless otherwise specified.
Example 1
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. 19.8kg (200.0 mol) of N-methylpyrrolidone, 9.8kg (98 mol) of 40% sodium hydroxide aqueous solution and 14.02kg (100.0 mol) of 40% sodium hydrosulfide aqueous solution are added into a 100L reaction kettle, the temperature is raised to 130 ℃ at a speed of 2.0 ℃/min under the stirring speed of 300rpm and the protection of nitrogen, then the temperature is raised to 160 ℃ at a speed of 0.5 ℃/min, finally the temperature is raised to 210 ℃ at a speed of 1 ℃/min, 14.22kg of aqueous solution (water content of 98.0%) is removed, the dehydration is completed, and the temperature is lowered to 160 ℃. At this time, the amount of sulfur in the system was 98.0mol and the water content was 117.6mol.
2. Adding 15.14kg (103.0 mol) of paradichlorobenzene and 13.2kg (133.0 mol) of NMP into the reaction kettle, heating to 260 ℃ at the speed of 0.5 ℃/min, preserving heat for 2 hours, then opening a valve of the polymerization kettle, heating to 280 ℃ through a heat exchanger, reducing the pressure to 0.8MPa through a regulating valve, heating to 280 ℃ through the heat exchanger, reducing the pressure to 0.5MPa through the regulating valve, mixing with nitrogen with the pressure of 0.5MPa and the temperature of 310 ℃ in a short pipe (mixing 1kg of reaction liquid with 0.6kg of nitrogen), discharging into a dryer with normal pressure through the regulating valve, and continuously drying until the temperature of the materials reaches 245 ℃ to start cooling to obtain a crude product.
3. 60kg of deionized water is added into the crude product, stirring is carried out for 3 hours, a filter cake is obtained after suction filtration, 50kg of deionized water is added, pH is added with acetic acid to regulate to 5, then the temperature is raised to 210 ℃, the temperature is kept for half an hour, the temperature is lowered, and the linear PPS product is obtained after suction filtration and drying.
4. The linear PPS is crosslinked at 220 ℃ under the oxygen content of 2 percent until the MFR reaches 300g/10min, and then the temperature is quickly reduced, so that the crosslinked PPS product is obtained.
Example 2
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. as in example 1.
2. Adding 15.14kg (103.0 mol) of paradichlorobenzene and 13.2kg (133.0 mol) of NMP into the reaction kettle, heating to 260 ℃ at the speed of 0.5 ℃/min, preserving heat for 2 hours, then opening a valve of the polymerization kettle, heating to 280 ℃ through a heat exchanger, reducing the pressure to 0.8MPa through a regulating valve, heating to 280 ℃ through the heat exchanger, reducing the pressure to 0.5MPa through the regulating valve, exchanging heat to 270 ℃ through the heat exchanger, discharging into a normal-pressure dryer through the regulating valve, continuously drying until the temperature of the materials reaches 245 ℃, and cooling to obtain a crude product.
3. As in example 1.
4. As in example 1.
Example 3
1. As in example 1.
2. Adding 15.14kg (103.0 mol) of paradichlorobenzene and 13.2kg (133.0 mol) of NMP into the reaction kettle, heating to 260 ℃ at the speed of 0.5 ℃/min, preserving heat for 2 hours, then opening a valve of the polymerization kettle, heating to 280 ℃ through a heat exchanger, reducing the pressure to 0.8MPa through a regulating valve, mixing with nitrogen with the pressure of 0.8MPa and 310 ℃ in a short pipe (mixing 1kg of reaction liquid with 0.6kg of nitrogen), discharging into a normal-pressure dryer through the regulating valve, continuously drying until the temperature of the materials reaches 245 ℃, and cooling to obtain a crude product.
3. As in example 1.
4. As in example 1.
Example 4
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. 19.8kg (200.0 mol) of NMP, 10.2kg (102 mol) of 40% sodium hydroxide aqueous solution and 14.02kg (100.0 mol) of 40% sodium hydrosulfide aqueous solution are added into a 100L reaction kettle, the temperature is raised to 130 ℃ at the speed of 2.0 ℃/min under the stirring speed of 300rpm and the protection of nitrogen, then the temperature is raised to 160 ℃ at the speed of 0.5 ℃/min, finally the temperature is raised to 210 ℃ at the speed of 1 ℃/min, 14.47kg of aqueous solution (the water content of which is 98.0%) is removed, the dehydration is completed, and the temperature is lowered to 160 ℃. At this time, the amount of sulfur in the system was 98.0mol and the water content was 117.6mol.
2. As in example 1.
3. As in example 1.
4. As in example 1.
Example 5
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. as in example 1.
2. 14.85kg (101.0 mol) of paradichlorobenzene and 13.2kg (133.0 mol) of NMP are added into the reaction kettle, the temperature is raised to 260 ℃ at the speed of 0.5 ℃/min, after the heat preservation is carried out for 2 hours, a valve of the polymerization kettle is started, the temperature is raised to 280 ℃ through a heat exchanger, the pressure is reduced to 0.8MPa through a regulating valve, the temperature is raised to 280 ℃ through the heat exchanger, the pressure is reduced to 0.5MPa through the regulating valve, the mixture is mixed with nitrogen with the pressure of 0.5MPa and the temperature of 310 ℃ in a short pipe (1 kg of reaction liquid is mixed with 0.6kg of nitrogen), the mixture is discharged into a dryer with normal pressure through the regulating valve, and then the mixture is continuously dried until the temperature of the material reaches 245 ℃ to start cooling, so as to obtain a crude product.
3. As in example 1.
4. As in example 1.
Example 6
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. as in example 1.
2. Adding 15.14kg (103.0 mol) of paradichlorobenzene into the reaction kettle, heating to 260 ℃ at the speed of 0.5 ℃/min for 2 hours after NMP (253.0 mol) is added, then opening a valve of the polymerization kettle, heating to 280 ℃ through a heat exchanger, reducing the pressure to 0.8MPa through a regulating valve, heating to 280 ℃ through the heat exchanger, reducing the pressure to 0.5MPa through the regulating valve, mixing with nitrogen with the pressure of 0.5MPa and the temperature of 310 ℃ in a short pipe (mixing 1kg of reaction liquid with 0.6kg of nitrogen), discharging into a normal-pressure dryer through the regulating valve, and continuously drying until the temperature of the materials reaches 245 ℃ to start cooling to obtain a crude product.
3. As in example 1.
4. As in example 1.
Example 7
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. as in example 1.
2. As in example 1.
3. 60kg of deionized water is added into the crude product, stirring is carried out for 3 hours, a filter cake is obtained after suction filtration, 50kg of deionized water is added, pH of acetic acid is added for 3.5 modulation, then the temperature is raised to 210 ℃, the temperature is kept for half an hour, the temperature is lowered, and the linear PPS product is obtained after suction filtration and drying.
4. As in example 1.
Example 8
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. as in example 1.
2. As in example 1.
3. As in example 1.
4. The linear PPS is crosslinked at 220 ℃ under the oxygen content of 2 percent until the MFR reaches 150, and then the temperature is quickly reduced, so that the crosslinked PPS product is obtained.
Example 9
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. as in example 1.
2. Adding 15.14kg (103.0 mol) of paradichlorobenzene and 13.2kg (133.0 mol) of NMP into the reaction kettle, heating to 260 ℃ at the speed of 0.5 ℃/min, preserving heat for 2 hours, then opening a valve of the polymerization kettle, heating to 280 ℃ through a heat exchanger, reducing the pressure to 0.8MPa through a regulating valve, heating to 280 ℃ through the heat exchanger, reducing the pressure to 0.5MPa through the regulating valve, mixing with nitrogen with the pressure of 0.5MPa and the temperature of 310 ℃ in a short pipe (mixing 1kg of reaction liquid with 0.6kg of nitrogen), discharging into a dryer with normal pressure through the regulating valve, and continuously drying until the temperature of the materials reaches 215 ℃ to start cooling to obtain a crude product.
3. As in example 1.
4. As in example 1.
Comparative example 1
The comparative example provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. as in example 1.
2. Adding 15.14kg (103.0 mol) of paradichlorobenzene and 13.2kg (133 mol) of NMP into the reaction kettle, heating to 260 ℃ at the speed of 0.5 ℃/min, preserving heat for 2 hours, quickly heating to 280 ℃, opening a valve of the polymerization kettle, discharging into a normal pressure dryer through a regulating valve, simultaneously introducing nitrogen with the pressure of 0.5MPa and 280 ℃, continuously drying after flash evaporation, and cooling to 245 ℃ to obtain a crude product.
3. As in example 1.
4. As in example 1.
Comparative example 2
The embodiment provides a crosslinked polyphenylene sulfide, which comprises the following specific steps:
1. as in example 1.
2. Adding 15.14kg (103.0 mol) of paradichlorobenzene and 13.2kg (133.0 mol) of NMP into the reaction kettle, heating to 260 ℃ at the speed of 0.5 ℃/min, preserving heat for 2 hours, quickly heating to 280 ℃, then opening a valve of the polymerization kettle, discharging the materials into a normal-pressure dryer through a regulating valve, continuously drying until the temperature of the materials reaches 245 ℃, and beginning cooling to obtain a crude product.
3. As in example 1.
4. As in example 1.
Test example 1
The crosslinked polyphenylene sulfide obtained in examples 1 to 9 and comparative examples 1 to 2 was subjected to performance test, specifically including MFR value, ash and volatile components. Melt Flow Rate (MFR) test: the melt flowability of the PPS resin was measured by using GOTTFERT MI-2.2, germany, with reference to national standard GB/T3682-2000, at 315.6 ℃. Weighing 8g of dried sample, quickly adding the sample into a charging barrel, compacting by a sample injection rod, adding a piston rod and a 5kg load weight, preheating for 5min, removing a lower thimble to allow the sample to naturally flow downwards, cutting off by scissors when the scale mark under the piston rod just disappears in the sight line, catching the effluent by a bowl, starting timing by a stopwatch, cutting off again by scissors when the scale mark on the piston rod disappears in the sight line, stopping timing, and removing the bowl. The mass M of the sample was weighed using a balance, and the recording time t(s) of the stopwatch was read, MFR (g/10 min) =m×600/t.
Ash test: the porcelain crucible is put into a muffle furnace with constant temperature of 750 ℃ to be burned to constant weight, then is taken out and put into a dryer to be cooled, and is weighed and marked as M0. 3g of the sample was weighed into a crucible, 10ml of nitric acid was added, and the mixture was placed on an alcohol burner until no smoke was emitted. Finally, the crucible is placed in a muffle furnace with constant temperature of 750 ℃ to be burned for 1h, taken out and placed in a dryer to be cooled, and then weighed, and recorded as M1. The resin ash content is (M1-M0)/3 x 100%.
Volatile component test: 3g of the sample is weighed and placed in a dried glass dish with the mass of M0, the glass dish is placed in a vacuum oven, the vacuum is pumped to 5kpa absolute, then the temperature is raised to 300 ℃, the temperature is kept for 2 hours, the temperature is reduced, the vacuum is broken, and the mass of the glass dish containing the sample is weighed and recorded as M1. The mass content of the volatile component is (3+M0-M1)/3×100%.
The results obtained are shown in Table 1.
TABLE 1
As can be seen from table 1, compared with the direct flash evaporation and discharging of reactants, the high-temperature gas is mixed before the dryer after multiple heating-decompression cycles, which is beneficial to reducing the contents of volatile components and ash in linear and crosslinked products; compared with the method that high-temperature gas is introduced into the dryer, the effect of mixing the high-temperature gas before drying is better; in the feed formulation, higher amounts of alkali do not affect the volatile and ash content of the linear PPS product, but can result in higher volatile content in the product when crosslinked to the same MFR due to the impact on the crosslinking process; the higher solvent content can lead to more residual solvent and low-boiling residues when entering a dryer, the atomization drying effect is poorer, the lower molar ratio of paradichlorobenzene to a sulfur source can lead to higher viscosity of reaction liquid, more difficult atomization and heat transfer, thicker product particles and fewer pore channels in the particles, and higher volatile components and ash content in the linear PPS product or the crosslinked PPS product; the crude product is insufficiently dried after flash evaporation, which is reflected in that the temperature of the material is not effectively improved and the content of volatile impurities is naturally higher; the lower pH is beneficial to ash removal during high-temperature acid washing, but can lead to more volatile impurities; more volatile components can be removed under longer heat-oxygen treatment time, but the fluidity of the product is greatly reduced, and the application in the downstream injection molding field is difficult when the fluidity is too low.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; while the invention has been described in detail with reference to the foregoing embodiments, it will be appreciated by those skilled in the art that variations may be made in the techniques described in the foregoing embodiments, or equivalents may be substituted for in part or in whole; such modifications and substitutions do not depart from the spirit of the invention.
Claims (11)
1. The preparation method of the low-volatile crosslinked polyphenylene sulfide is characterized by comprising the following steps of:
A. mixing a sulfur source, an alkali solution and a solvent, heating for dehydration, and adding a dihalogen aromatic compound and the solvent for polymerization reaction after dehydration;
B. after the polymerization reaction is finished, directly discharging without cooling, and enabling the materials to enter a dryer after being subjected to multiple heating temperature rise-decompression cycles in a discharging pipeline, and continuously drying to obtain a polyphenylene sulfide crude product;
C. washing and purifying the polyphenylene sulfide crude product to obtain linear polyphenylene sulfide;
D. the linear polyphenylene sulfide is subjected to heat treatment or thermal oxygen treatment to reduce volatile matters so as to obtain the low-volatile crosslinked polyphenylene sulfide.
2. The method according to claim 1, wherein in the step B, the number of "heating up-depressurizing" cycles is not less than 2;
preferably, the number of the heating temperature rise-decompression cycles is 3, specifically: and heating the reactant by a first heater, then performing first decompression, continuing to heat by a second heater, then performing second decompression, finally performing third decompression after heating by a third heater, and feeding the reactant subjected to multiphase mixing into a dryer, and continuously drying to obtain a polyphenylene sulfide crude product.
3. The production method according to claim 2, wherein the first heating temperature and the second heating temperature are each independently 270 ℃ to 290 ℃;
preferably, the pressure after the first decompression is 0.7MPa to 0.9MPa;
preferably, the pressure after the second decompression is 0.45MPa to 0.6MPa;
preferably, the pressure after the third pressure reduction is normal pressure.
4. The production method according to claim 2, wherein the third heating is performed by mixing with a high-temperature non-reactive gas;
preferably, the temperature of the high temperature non-reactive gas is 280 ℃ to 320 ℃;
preferably, the high temperature non-reactive gas is used in an amount of 25% to 100% by mass of the reaction mixture;
preferably, the high temperature non-reactive gas is nitrogen or water vapor.
5. The method according to claim 2, wherein the temperature of the drying is 240-260 ℃ and the material is dried until the temperature of the material reaches above 240 ℃.
6. The method according to claim 1, wherein in step D, the heat treatment under the protection of inert gas or the thermal oxygen treatment process;
preferably, the temperature of the heat treatment is 200 ℃ to 240 ℃;
preferably, the temperature of the thermal oxygen treatment is 200-240 ℃, and the volume content of oxygen is 2-10%;
preferably, in step a, the temperature of the polymerization reaction is 240 ℃ to 270 ℃.
7. The process according to claim 1, wherein in step A, the dehydrated liquid is obtained after the dehydration at elevated temperature, wherein H in the dehydrated liquid is calculated as 1mol of sulfur source 2 The molar ratio of O to sulfur source is 1.0-1.5;
preferably, in the step A, after the dihaloaromatic compound and the solvent are added and before the polymerization, the molar ratio of the reaction solvent to the sulfur source is 3.0 to 4.0, based on 1mol of the sulfur source;
preferably, in step A, the molar ratio of base to sulfur source is from 0.96 to 1.00, based on 1mol of sulfur source;
preferably, the molar ratio of dihaloaromatic compound to sulfur source is from 1.04 to 1.10, based on 1mol of sulfur source.
8. The method of any one of claims 1-6, wherein the sulfur source comprises a sulfur hydride;
preferably, the alkali solution comprises a sodium hydroxide solution or a potassium hydroxide solution;
preferably, the solvent comprises an organic amide;
preferably, the organic amide comprises N-methylpyrrolidone;
preferably, the dihaloaromatic compound comprises p-dichlorobenzene.
9. The method according to any one of claims 1 to 6, wherein in step C, the water washing includes normal pressure water washing and high temperature water washing;
preferably, the temperature of the high-temperature water washing is 180-220 ℃;
preferably, the pH of the slurry mixture of the crude product and water before high temperature washing is 4.5-5.5.
10. A low volatile cross-linked polyphenylene sulfide prepared by the method of any one of claims 1 to 9.
11. The low-volatile crosslinked polyphenylene sulfide according to claim 10, characterized in that the MFR value is 100-1000, preferably 100-500;
preferably, the ash content of the low volatile crosslinked polyphenylene sulfide is < 0.25wt.%, preferably < 0.15wt.%;
preferably, the low-volatile crosslinked polyphenylene sulfide has a volatile component content of <
0.40wt.%, preferably < 0.2wt.%.
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| US5247063A (en) * | 1987-04-24 | 1993-09-21 | Bayer Aktiengesellschaft | Process for the purification of polyarylene sulphides |
| JPH0853621A (en) * | 1994-08-11 | 1996-02-27 | Toray Ind Inc | Polyphenylene sulfide resin and molded product thereof |
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| CN101910251A (en) * | 2007-11-08 | 2010-12-08 | 东丽株式会社 | Process for production of polyphenylene sulfide resin |
| KR20210089888A (en) * | 2020-01-09 | 2021-07-19 | 주식회사 엘지화학 | Process for preparation of polyphenylene sulfide |
| CN115279734A (en) * | 2019-12-20 | 2022-11-01 | 提克纳有限责任公司 | Method of forming polyarylene sulfide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5247063A (en) * | 1987-04-24 | 1993-09-21 | Bayer Aktiengesellschaft | Process for the purification of polyarylene sulphides |
| JPH0853621A (en) * | 1994-08-11 | 1996-02-27 | Toray Ind Inc | Polyphenylene sulfide resin and molded product thereof |
| JP2003048982A (en) * | 2001-08-08 | 2003-02-21 | Toray Ind Inc | Polyphenylene sulfide resin, polyphenylene sulfide film and method for producing them |
| CN101910251A (en) * | 2007-11-08 | 2010-12-08 | 东丽株式会社 | Process for production of polyphenylene sulfide resin |
| CN115279734A (en) * | 2019-12-20 | 2022-11-01 | 提克纳有限责任公司 | Method of forming polyarylene sulfide |
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