CN115073739A - Preparation method, product and application of crosslinked polyphenylene sulfide - Google Patents
Preparation method, product and application of crosslinked polyphenylene sulfide Download PDFInfo
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- CN115073739A CN115073739A CN202210801993.7A CN202210801993A CN115073739A CN 115073739 A CN115073739 A CN 115073739A CN 202210801993 A CN202210801993 A CN 202210801993A CN 115073739 A CN115073739 A CN 115073739A
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- polyphenylene sulfide
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 79
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title description 6
- 238000005406 washing Methods 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000047 product Substances 0.000 claims abstract description 35
- 239000012043 crude product Substances 0.000 claims abstract description 28
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 230000008020 evaporation Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 13
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000003857 carboxamides Chemical class 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000004132 cross linking Methods 0.000 claims description 47
- 238000004519 manufacturing process Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000004537 pulping Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000003889 chemical engineering Methods 0.000 claims 1
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000003756 stirring Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000428 dust Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052573 porcelain Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- ZOCLAPYLSUCOGI-UHFFFAOYSA-M potassium hydrosulfide Chemical compound [SH-].[K+] ZOCLAPYLSUCOGI-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G75/0259—Preparatory processes metal hydrogensulfides
-
- 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
-
- 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
-
- 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
- C08G75/0286—Chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
- C08J2381/02—Polythioethers; Polythioether-ethers
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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)
- General Chemical & Material Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a method for preparing cross-linked polyphenylene sulfide, which comprises the following steps: (1) dehydrating a sulfur source, an alkali metal hydroxide and an organic amide solvent, then adding a dihalogen aromatic compound and the organic amide solvent for polymerization reaction, and after the reaction is finished, carrying out solid-liquid separation by flash evaporation to obtain a salt-containing crude product; (2) washing and drying the salt-containing crude product at normal pressure, and then carrying out thermal oxidation treatment to obtain a cross-linked product crude product; (3) and (3) washing the crosslinked crude product at high temperature, and drying to obtain the crosslinked polyphenylene sulfide. The method can effectively reduce the ash content of the PPS cross-linked product to be less than 0.5 wt% at a lower high-temperature water washing temperature while keeping higher thermal oxidation treatment efficiency. The invention also provides a cross-linked product obtained by the method and application thereof.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method, a product and application of crosslinked polyphenylene sulfide.
Background
Currently, commercially available PPS (polyphenylene sulfide) resins are mainly classified into two types, i.e., linear PPS resins and crosslinked PPS resins, in view of their chain structure. The linear PPS resin is directly obtained by high-temperature high-pressure polymerization, separation and purification, and the crosslinking resin is prepared by further carrying out thermal-oxidative crosslinking on the linear PPS resin. According to different solid-liquid separation modes, the conventional preparation method of the linear PPS resin can be mainly divided into a cooling crystallization process and a flash evaporation process, although the polymerization preparation method of linear raw powder for preparing the crosslinking PPS resin is not limited, but in practice, most of the conventional commercial crosslinking PPS resins use the flash evaporation process to prepare the required linear crosslinking raw powder, and after a solvent is separated by flash evaporation, the linear crosslinking raw powder is subjected to washing and purification for many times, and is dried and then subjected to thermal oxidation treatment to reach a target value. The Melt Fluidity (MFR) of the resin is continuously reduced in the thermal-oxidative crosslinking process until the melt fluidity reaches a target value, the resin is cooled and stops crosslinking, and a product is discharged, and the treatment time required by the thermal-oxidative crosslinking of the resin is relatively long, so that the production efficiency of a crosslinked product is greatly influenced, particularly under the condition that the target MFR is low.
A typical production method of polyphenylene sulfide (PPS) is a production method in which sodium sulfide/sodium hydrosulfide and p-dichlorobenzene are subjected to a high-temperature polymerization reaction in the presence of high-concentration sodium hydroxide in N-methylpyrrolidone (NMP). Despite the multiple washing and purification, a certain amount of metal ions remain in the PPS product, which constitute ash of the product and impair the properties, particularly the electrical properties, of the PPS product, and these metal ions remain as a by-product of residual sodium chloride, sodium ion end groups, and sodium ion-containing small-molecule organic salts. Particularly, compared with the temperature-reducing crystallization process, in the flash evaporation process, because the small-molecular organic salt byproduct can only be removed through a washing process, the washing difficulty of the byproduct sodium chloride is relatively large, the molecular weight is relatively low, and the like, the subsequent washing and purification processes usually comprise one-step high-temperature washing, the washing effect is greatly influenced by the washing temperature, but the washing effect is limited by the problems of pressure and medium corrosivity, the washing temperature is below 220 ℃, and the ash content of the final product is still relatively high.
JP1987325279(EP1988312268) reports that when a PPS product is obtained by re-dissolving a PPS precursor obtained by polymerization in NMP, adding sodium hydroxide, holding the temperature for a certain period of time, separating and washing the product, the crosslinking speed of the treated PPS resin is remarkably increased, but the method causes the ash content of the product to be increased and the solvent loss during the production process to be increased.
Patent JP1989240529A reports that the high-pressure acid washing treatment of PPS resin during the post-treatment of PPS after the end of polymerization significantly reduces the ash content of the product and significantly accelerates the crosslinking speed of linear PPS raw powder. However, the acid washing can obviously improve the fluidity of the resin and simultaneously reduce the thermal stability of the resin, and the gel content in the cross-linked product finally obtained after the thermal oxidation treatment is higher. In addition, high temperature pickling has higher requirements on the corrosion resistance of equipment.
Chinese patent application with publication number CN 114479082A discloses a clean production process of polyphenylene sulfide, wherein a polyphenylene sulfide reaction solution is subjected to flash evaporation to obtain a solid, then deionized water is used for washing the solid twice under normal pressure, and the washed solid is dried to obtain a linear polyphenylene sulfide product.
Disclosure of Invention
In the research on the PPS washing and purifying process in the prior art, the inventor of the application finds that most of by-products, namely sodium chloride, residual sodium sulfide and partial small-molecule water-soluble by-products are washed away in normal-pressure washing, and then most of water-soluble by-products are washed away in high-temperature washing, and meanwhile, partial ionized active end groups are broken or replaced, which is also the reason that linear polyphenylene sulfide product ash can be further reduced in high-temperature washing, and the ash reduction effect is obviously influenced by the temperature of the high-temperature washing. However, the inventors of the present application have unexpectedly found that after washing with high-temperature water, the efficiency of the thermo-oxidative treatment of the linear polyphenylene sulfide product decreases, resulting in a longer time required for crosslinking to the same MFR. The inventors of the present application have also found that during the thermal oxidation treatment, the ionized end groups of the PPS are also destroyed and fall off, so that the ash content of the product can be further reduced more easily by further washing with water at high temperature.
The technical problem to be solved by the invention is as follows: the method can effectively reduce the ash content of the PPS cross-linked product to be less than 0.5 wt% at a lower high-temperature water washing temperature while keeping higher thermal oxidation treatment efficiency.
In view of the above problems, the present invention provides a method for producing a crosslinked polyphenylene sulfide, comprising:
(1) dehydrating a sulfur source, an alkali metal hydroxide and an organic amide solvent, then adding a dihalogen aromatic compound and the organic amide solvent for polymerization reaction, and after the reaction is finished, carrying out solid-liquid separation by flash evaporation to obtain a salt-containing crude product;
(2) washing and drying the salt-containing crude product at normal pressure, and then carrying out thermal oxidation treatment to obtain a cross-linked product crude product;
the temperature of the normal-pressure water washing is 30-70 ℃, and preferably 30-65 ℃;
(3) washing the crosslinked crude product with high-temperature water, and drying to obtain the crosslinked polyphenylene sulfide;
the temperature of the high-temperature water washing is 120-180 ℃.
The dehydration and polymerization in step (1) are the prior art, and the specific reaction conditions and reaction process can refer to the prior art such as CN 114479082A.
Preferably, the sulfur source is selected from a sulfide or hydrosulfide, preferably sodium sulfide, sodium hydrosulfide or potassium hydrosulfide.
Preferably, the alkali metal hydroxide is NaOH or KOH, more preferably NaOH. The amount of the alkaline substance is 1.00-1.20mol based on 1.0mol of total sulfur.
Preferably, the organic amide solvent N-methyl pyrrolidone is 2.5 to 4.5mol of the total amount of the solvent based on 1.0mol of the total sulfur.
Preferably, the dihalo aromatic compound is p-dichlorobenzene.
Preferably, the temperature of the polymerization reaction is 220-280 ℃.
Preferably, in the step (2), the mass ratio of water to the salt-containing crude product in normal-pressure water washing is 2-5: 1.
preferably, in the step (2), the temperature of the washing with water under normal pressure is 30 to 50 ℃.
Preferably, in the step (2), the drying temperature is 100-160 ℃.
Preferably, in the step (2), the thermal oxidation treatment temperature is 200-230 ℃, and more preferably 200-220 ℃; the oxygen content in the crosslinking atmosphere is 8 to 21%, more preferably 12 to 21%, and still more preferably 15 to 21%.
Preferably, in the step (3), the high-temperature water washing mode is water adding and pulping treatment, and the mass ratio of water to the cross-linked product crude product is 4-10: 1.
preferably, in the step (3), the temperature of the high-temperature water washing is 150 to 180 ℃.
Preferably, in the step (3), the drying temperature is 100-160 ℃.
The invention also provides the cross-linked polyphenylene sulfide which is obtained by the preparation method, the ash content of the cross-linked polyphenylene sulfide is below 0.5 wt%, and the MFR value of the cross-linked polyphenylene sulfide is below 240g/10 min.
Preferably, the ash content of the polyphenylene sulfide prepared by the invention is between 0.43 and 0.49 wt%, and the MFR value of the crosslinking type polyphenylene sulfide is between 120g/10min and 280g/10 min. More preferably, the ash content of the polyphenylene sulfide prepared by the invention is between 0.43 and 0.46 weight percent, and the MFR value of the crosslinking type polyphenylene sulfide is between 120g/10min and 240g/10 min.
The invention also provides application of the cross-linked polyphenylene sulfide, and the cross-linked polyphenylene sulfide is applied to the fields of automobile parts, electronic/electrical equipment, chemical industry and mechanical industry.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention carries out thermal oxidation treatment after two times of normal pressure water washing, avoids the damage to the ionized active end group during high temperature washing, and can prepare the PPS cross-linked product with low MFR with higher thermal oxidation treatment efficiency;
(2) the invention carries out high-temperature washing after the thermal oxidation treatment, and can achieve better ash removal effect at lower washing temperature.
Detailed Description
Melt Flow Rate (MFR) test: the melt flowability of the PPS resin was measured using a German GOTTFERT MI-2.2 with reference to the national standard GB/T3682-2000 at a test temperature of 315.6 ℃. Weighing 8g of dried sample, quickly adding the sample into a charging barrel, compacting by using a sample introduction rod, adding a piston rod and a 5kg load weight, preheating for 5min, then removing a thimble at the lower part, allowing the sample to naturally flow downwards, when the lower scale line of the piston rod just disappears in a sight line, cutting off the sample by using scissors, catching the effluent by using a bowl, starting timing by using a stopwatch, when the upper scale line of the piston rod disappears in the sight line, cutting off the sample by using the scissors again, stopping timing, and removing the bowl. When the weight M (g) of the sample is used and the recording time t(s) of the stopwatch is read, the MFR (g/10min) is M x 600/t.
Ash content test: putting the porcelain crucible into a muffle furnace with the constant temperature of 750 ℃ to be burnt to constant weight, taking out the porcelain crucible, putting the porcelain crucible into a dryer to be cooled, weighing the porcelain crucible, and recording the weight as M 0 . 3g of the sample was weighed into a crucible, 10ml of nitric acid was added, and the mixture was then fired on an alcohol burner until no further smoke was emitted. Finally, the crucible is placed in a muffle furnace with constant temperature of 750 ℃ to be burned for 1h, the crucible is taken out and placed in a drier to be weighed after being cooled, and the weight is recorded as M 1 . Resin ash content (M) 1 -M 0 )/3*100％。
Example 1
Adding 19.8kg (200.0mol) of N-methylpyrrolidone and 10.2kg (102.0mol) of 40% sodium hydroxide aqueous solution into a 100L reaction kettle, adding 14.02kg (100.0mol) of 40% sodium hydrosulfide aqueous solution, heating to 130 ℃ at the speed of 2.0 ℃/min under the stirring speed of 300rpm and the protection of nitrogen, heating to 160 ℃ at the speed of 0.5 ℃/min, heating to 210 ℃ at the speed of 1 ℃/min, removing 14.50kg of aqueous solution (the water content is 98.0 percent), removing dehydration, and cooling to 160 ℃. At this time, the amount of sulfur in the system was 98.0mol, and the water content was 117.6 mol.
Adding 15.14kg (103.0mol) of p-dichlorobenzene and 13.17kg (133mol) of NMP into the reaction kettle, heating to 260 ℃ at the speed of 0.5 ℃/min, preserving heat for 3 hours, then carrying out flash evaporation to a flash tank, after the flash evaporation is finished, continuously drying for 1 hour in a nitrogen atmosphere, fully removing the NMP, wherein the drying temperature is 220 ℃, and obtaining 20.9kg of crude product.
Adding 50kg of deionized water into the dried flash evaporation crude product, fully stirring and washing at 65 ℃, filtering, adding 50kg of deionized water into the filter cake again, repeatedly washing once, and drying the filter cake. And (2) placing the dried PPS into a crosslinking bin with a stirring and dust removing bag and a heat conduction oil jacket, introducing crosslinking gas with the oxygen content of 16% at 220 ℃ for treatment for 12 hours, then adding 50kg of deionized water for repulping, heating to 150 ℃ under the condition of pressurization, preserving heat for half an hour, then cooling and filtering, and finally drying to obtain a PPS crosslinked product CPPS-1, wherein the test MFR is 230g/10min, and the ash content is 0.46 wt%.
Example 2
The dried PPS after the secondary normal pressure washing is prepared according to the method in the embodiment 1, the dried PPS is placed in a crosslinking bin with a stirring bag, a dust removal bag and a heat conduction oil jacket, crosslinking gas with 16 percent of oxygen content is introduced at 220 ℃ for treatment for 30 hours, then 50kg of deionized water is added for re-pulping, the temperature is raised to 150 ℃ under the pressurization condition, the temperature is kept for half an hour, then the temperature is reduced for filtration, and finally the PPS crosslinked product CPPS-2 is obtained after drying, the MFR is 120g/10min, and the ash content is 0.43 wt%.
Example 3
The flash evaporation crude product is prepared according to the method in the embodiment 1, then 50kg of deionized water is added into the dried flash evaporation crude product, the mixture is fully stirred and washed at 65 ℃ and then filtered, 50kg of deionized water is added into the filter cake again, the washing is repeated once, and then the filter cake is dried. And (2) placing the dried PPS into a crosslinking bin with a stirring and dust removing bag and a heat conduction oil jacket, introducing crosslinking gas with 16 percent of oxygen content at 220 ℃ for treatment for 12 hours, then adding 50kg of deionized water for pulping again, heating to 180 ℃, preserving heat for half an hour, then cooling and filtering, and finally drying to obtain a PPS crosslinked product CPPS-3, wherein the test MFR is 240g/10min, and the ash content is 0.44 wt%.
Examples 1 and 3 show that the ash is more easily washed away after thermal oxygen crosslinking, and higher washing temperatures have no significant effect on reducing the ash.
Example 4
The flash evaporation crude product is prepared according to the method in the embodiment 1, 50kg of deionized water is added into the dried flash evaporation crude product, the mixture is fully stirred and washed at 65 ℃ and then filtered, 50kg of deionized water is added into the filter cake again, the washing is repeated once, and then the filter cake is dried. And (2) placing the dried PPS into a crosslinking bin with a stirring and dust removing bag and a heat conduction oil jacket, introducing crosslinking gas with the oxygen content of 16% at 200 ℃ for treatment for 24 hours, then adding 50kg of deionized water for pulping again, heating to 150 ℃, preserving heat for half an hour, then cooling and filtering, and finally drying to obtain a PPS crosslinked product CPPS-4, wherein the MFR is 280g/10min and the ash content is 0.49 wt%.
Comparative example 1
The dried flash evaporation crude product obtained according to the method of the embodiment 1 is added with 50kg of deionized water, fully stirred and washed at 65 ℃ and then filtered, 50kg of deionized water is added into the filter cake again, the washing is repeated once, then 50kg of deionized water is added for pulping, the temperature is raised to 150 ℃, the temperature is kept for half an hour, the temperature is reduced and then the filter cake is filtered, the washed filter cake is dried, the dried PPS is placed in a crosslinking bin with a stirring and dust removing bag and a heat conduction oil jacket, crosslinking gas with 16 percent of oxygen content is introduced at 220 ℃ for treatment for 12 hours, the PPS crosslinked product CPPS-5 is obtained, the MFR is 440g/10min, and the ash content is 0.65 wt%.
Comparative example 2
The dried flash evaporation crude product obtained according to the method in the embodiment 1 is added with 50kg of deionized water, fully stirred and washed at 65 ℃ and then filtered, 50kg of deionized water is added into a filter cake again, the washing is repeated once, 50kg of deionized water is added for pulping, the temperature is raised to 200 ℃, the temperature is kept for half an hour, the temperature is reduced and then filtered, the washed filter cake is dried, the dried PPS is placed in a crosslinking bin with a stirring and dust removing bag and a heat conduction oil jacket, crosslinking gas with 16 percent of oxygen content is introduced at 220 ℃ for treatment for 12 hours, and a PPS crosslinking product CPPS-6 is obtained, wherein the test MFR is 550g/10min, and the ash content is 0.54 wt%.
The results of comparative example 1 and comparative example 2 show that performing a high-temperature water washing before the thermal-oxidative crosslinking treatment decreases the efficiency of thermal-oxidative crosslinking, and particularly that the temperature of the high-temperature water washing increases, resulting in a further increase in MFR.
Comparative example 3 (according to the method of CN 114479082A, no high-temperature washing after crosslinking)
The dried flash evaporation crude product obtained according to the method of the embodiment 1 is added with 50kg of deionized water, fully stirred and washed at 100 ℃ and then filtered, 50kg of deionized water is added into the filter cake again, the washing is repeated once, the washed filter cake is dried, the dried PPS is placed in a crosslinking bin with a stirring, dust removal bag and a heat conduction oil jacket, and crosslinking gas with 12 percent of oxygen content is introduced at 240 ℃ for treatment for 12 hours, thus obtaining a PPS crosslinking product CPPS-7, wherein the MFR is 320g/10min and the ash content is 0.95 wt%.
Comparative example 4
The flash evaporation crude product is prepared according to the method in the embodiment 1, 50kg of deionized water is added into the dried flash evaporation crude product, the mixture is fully stirred and washed at 65 ℃ and then filtered, 50kg of deionized water is added into the filter cake again, the washing is repeated once, and then the filter cake is dried. And (2) placing the dried PPS into a crosslinking bin with a stirring and dust removing bag and a heat conduction oil jacket, introducing crosslinking gas with 16 percent of oxygen content at 190 ℃ for treatment for 12 hours, then adding 50kg of deionized water for pulping again, heating to 160 ℃, keeping the temperature for half an hour, then cooling and filtering, and finally drying to obtain a PPS crosslinked product CPPS-8, wherein the test MFR is 700g/10min, and the ash content is 0.58 wt%.
The results of comparative example 4 show that too low a crosslinking temperature leads to a decrease in crosslinking efficiency and too high an MFR value.
Comparative example 5
The flash evaporation crude product is prepared according to the method in the embodiment 1, 50kg of deionized water is added into the dried flash evaporation crude product, the mixture is fully stirred and washed at 65 ℃ and then filtered, 50kg of deionized water is added into the filter cake again, the washing is repeated once, and then the filter cake is dried. And (2) placing the dried PPS into a crosslinking bin with a stirring and dust removing bag and a heat conduction oil jacket, introducing crosslinking gas with the oxygen content of 8% at 250 ℃ for treatment for 12 hours, then adding 50kg of deionized water for pulping again, heating to 150 ℃, preserving heat for half an hour, then cooling and filtering, and finally drying to obtain a PPS crosslinked product CPPS-9, wherein the test MFR is 150g/10min, and the ash content is 0.61 wt%.
The results of comparative example 5 show that too high a temperature for thermo-oxidative crosslinking, while effective in reducing MFR values, results in increased ash.
Claims (10)
1. A method for producing a crosslinked polyphenylene sulfide, comprising:
(1) dehydrating a sulfur source, an alkali metal hydroxide and an organic amide solvent, then adding a dihalogen aromatic compound and the organic amide solvent for polymerization reaction, and after the reaction is finished, carrying out solid-liquid separation by flash evaporation to obtain a salt-containing crude product;
(2) washing and drying the salt-containing crude product at normal pressure, and then carrying out thermal oxidation treatment in a crosslinking atmosphere to obtain a crosslinked product crude product;
the temperature of the normal-pressure water washing is 30-70 ℃;
(3) washing the crosslinking product crude product at high temperature, and drying to obtain the crosslinking polyphenylene sulfide;
the temperature of the high-temperature water washing is 120-180 ℃.
2. The method for producing crosslinked polyphenylene sulfide according to claim 1, wherein the temperature of the high-temperature water washing is 150 to 180 ℃.
3. The method for producing crosslinked polyphenylene sulfide according to claim 1, wherein in the step (2), the mass ratio of water to the salt-containing crude product in the normal-pressure washing is 2 to 5: 1.
4. the method for producing crosslinked polyphenylene sulfide according to claim 1, wherein the temperature for drying in step (2) is 100 to 160 ℃.
5. The method for producing crosslinked polyphenylene sulfide according to claim 1, wherein in the step (2), the temperature of the thermal oxidation treatment is 200 to 230 ℃, and the oxygen content of the crosslinking atmosphere is 8 to 21%.
6. The method for producing crosslinked polyphenylene sulfide according to claim 5, wherein the oxygen content of the crosslinking atmosphere is 12 to 21%.
7. The method for preparing crosslinked polyphenylene sulfide according to claim 1, wherein in step (3), the high-temperature water washing is performed by adding water and pulping, and the mass ratio of water to the crude crosslinked product is 4-10: 1.
8. the method for producing crosslinked polyphenylene sulfide according to claim 1, wherein the temperature for drying in step (3) is 100 to 160 ℃.
9. A crosslinked polyphenylene sulfide obtained by the production method according to any one of claims 1 to 8;
the ash content of the crosslinked polyphenylene sulfide is less than 0.5 wt%, and the MFR value of the crosslinked polyphenylene sulfide is less than 240g/10 min.
10. The use of the crosslinked polyphenylene sulfide according to claim 9, wherein the crosslinked polyphenylene sulfide is used in the fields of automobile parts, electronic/electrical devices, chemical engineering, and mechanical industry.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172387A (en) * | 1999-12-21 | 2001-06-26 | Tonen Chem Corp | Method for producing polyarylene sulfide |
| JP2013159656A (en) * | 2012-02-02 | 2013-08-19 | Dic Corp | Crosslinked polyarylene sulfide resin and production method thereof |
| CN114479082A (en) * | 2021-12-30 | 2022-05-13 | 浙江新和成特种材料有限公司 | Clean production process of polyphenylene sulfide and treatment method of polyphenylene sulfide reaction liquid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001172387A (en) * | 1999-12-21 | 2001-06-26 | Tonen Chem Corp | Method for producing polyarylene sulfide |
| JP2013159656A (en) * | 2012-02-02 | 2013-08-19 | Dic Corp | Crosslinked polyarylene sulfide resin and production method thereof |
| CN114479082A (en) * | 2021-12-30 | 2022-05-13 | 浙江新和成特种材料有限公司 | Clean production process of polyphenylene sulfide and treatment method of polyphenylene sulfide reaction liquid |
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