CN118063773A - Production method of polyphenylene sulfide with low metal impurities - Google Patents
Production method of polyphenylene sulfide with low metal impurities Download PDFInfo
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- methylpyrrolidone
- polyphenylene sulfide
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 37
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 37
- 239000012535 impurity Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 32
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 12
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000012065 filter cake Substances 0.000 claims abstract description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 73
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 34
- 238000006297 dehydration reaction Methods 0.000 claims description 31
- 230000018044 dehydration Effects 0.000 claims description 30
- 238000011084 recovery Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- XWKIXFQOFAVHQI-UHFFFAOYSA-N disodium;sulfide;pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[S-2] XWKIXFQOFAVHQI-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004064 recycling Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229940117389 dichlorobenzene Drugs 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 230000000153 supplemental effect Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 229940031993 lithium benzoate Drugs 0.000 claims description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 2
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 230000019086 sulfide ion homeostasis Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 208000005156 Dehydration Diseases 0.000 description 24
- 239000000243 solution Substances 0.000 description 14
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- -1 alkali metal salt Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method 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
- C08G75/0277—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 discloses a method for producing polyphenylene sulfide with low metal impurities, and relates to the technical field of polyphenylene sulfide production. Sodium sulfide and paradichlorobenzene are used as raw materials, and lithium chloride and caprolactone are used as catalysts; the polymerization reaction is divided into two stages, volatile caprolactone is used as a catalyst in one reaction stage, the temperature is controlled to be raised to 180-190 ℃ for carrying out the first-stage reaction, the temperature is raised to 225-235 ℃ after the first-stage reaction is finished and is used for removing caprolactone in a solution system for a period of time, then lithium chloride is added and the temperature is kept at 225-235 ℃ for carrying out the second-stage reaction, after the second-stage reaction is finished, the material is discharged after cooling according to a cooling program, the material is filtered after discharging, and a filter cake is washed by deionized water, dehydrated and dried in vacuum to obtain the product. According to the invention, the lithium ion coated in the molecular chain in the polymerization reaction process is reduced as a whole by adopting different catalysts for catalysis in two stages of the polymerization reaction, so that the polyphenylene sulfide with low metal impurities is obtained.
Description
Technical Field
The invention belongs to the technical field of polyphenylene sulfide production, and particularly relates to a method for producing polyphenylene sulfide with low metal impurities.
Background
The polyphenylene sulfide has excellent thermal stability, chemical stability, corrosion resistance and electrical property, has good affinity with various inorganic fillers, and can be compounded with various inorganic fillers and other high polymer materials to prepare engineering plastics and blend alloys with excellent properties. The sodium sulfide method is a common synthesis method of polyphenylene sulfide at present, and particularly uses paradichlorobenzene and anhydrous sodium sulfide to prepare PPS through condensation reaction in a polar solvent. The method takes anhydrous sodium sulfide and 1, 4-dichlorobenzene as raw materials, alkali metal salt as an auxiliary agent, and prepares PPS through reaction polycondensation in a strong polar proton solvent.
The method for recycling auxiliary lithium chloride used in the polyphenylene sulfide resin production process is disclosed in CN104877167A, and comprises the following steps: ⑴ Dissolving sodium sulfide in NMP, removing water in the sodium sulfide by inert gas protection under the catalysis of lithium chloride and caustic soda flakes, and adding DCB and NMP solution for polymerization reaction to synthesize polyphenylene sulfide resin mixture slurry; ⑵ Carrying out solid-liquid separation on the polyphenylene sulfide resin mixture slurry to respectively obtain a polyphenylene sulfide resin product containing an oligomer, byproduct salt and NMP solution containing lithium chloride; ⑶ The NMP solution containing lithium chloride is subjected to filter pressing, purification and purification to obtain NMP solution containing 75-85% of lithium chloride; ⑷ The polyphenylene sulfide resin product containing the oligomer and the byproduct salt are subjected to reverse soaking and rinsing to respectively obtain the polyphenylene sulfide resin, the byproduct salt and rinsing liquid; ⑸ Distilling and separating rinsing liquid under reduced pressure to obtain NMP salt solution; ⑹ And desalting the NMP salt solution to obtain NMP solution containing 10-20% of lithium chloride. In the above, although the recycling of lithium chloride is realized, in a specific production process, along with the polymerization of polyphenylene sulfide, lithium ions contained in a solution system are "wrapped" in a macromolecular chain of a produced resin, so that a large amount of lithium ions are contained in the prepared polyphenylene sulfide resin, and the "wrapped" lithium ions cannot be removed by a subsequent washing method with deionized water or the like, so that a large amount of metal impurities are contained in the polyphenylene sulfide.
Disclosure of Invention
The invention aims to provide a method for producing low-metal-impurity polyphenylene sulfide, which reduces the amount of lithium ions wrapped in a molecular chain in the polymerization reaction process as a whole by adopting different catalysts for catalysis in two stages of the polymerization reaction, and solves the problem that the prepared polyphenylene sulfide contains a large amount of metal impurities.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention relates to a method for producing polyphenylene sulfide with low metal impurities, which comprises the following steps:
Step 1, adding sodium sulfide pentahydrate, sodium hydroxide and N-methylpyrrolidone into a magnetic stirring reaction kettle, uniformly stirring, and keeping until the dehydration rate reaches 85-90% under the protection of nitrogen;
step 2, putting dichlorobenzene, a catalyst A and N-methylpyrrolidone into a p-dichlorobenzene dissolution kettle, starting stirring, and heating the system to 70-150 ℃ under the protection of nitrogen until the p-dichlorobenzene is dissolved in the N-methylpyrrolidone to obtain a solution A;
Step 3, adding the obtained solution A into the dehydration system obtained in the step 1, controlling the temperature to be raised to 180-190 ℃ and reacting at constant temperature for T1 time to perform a first-stage reaction; heating to 225-235 ℃ for T2, adding a solution B dissolved with a catalyst B, and performing a second-stage reaction in a constant-temperature reaction T3 time;
step 4, discharging after cooling according to a cooling program, filtering after discharging, washing a filter cake with deionized water, dehydrating and vacuum drying to obtain a product;
The catalyst A is caprolactam or caprolactone; the catalyst B is alkali metal acetate, lithium chloride, magnesium chloride, aluminum chloride, lithium benzoate, lithium stearate or lithium acetate.
Further, the molar ratio of the sodium sulfide pentahydrate to the N-methylpyrrolidone in the step1 is 1:3.0-3.5.
Further, in the step 1, the temperature is firstly increased to 210-215 ℃ for dehydration, when the dehydration rate reaches 65-75%, the temperature is naturally reduced to 130-135 ℃ and then the temperature is kept constant until the dehydration rate reaches 85-90% for standby.
Further, in the step 1, N-methyl pyrrolidone heated to 70-80 ℃ is added into the magnetic stirring reaction kettle in a supplementary manner while dewatering.
Further, in the step 1, the loss amount of N-methylpyrrolidone is obtained by metering N-methylpyrrolidone carried out by nitrogen flow, and then N-methylpyrrolidone corresponding to the loss amount is added into the magnetic stirring reaction kettle in a supplementing manner.
Further, the calculation method of the loss amount of the N-methyl pyrrolidone comprises the steps of condensing and recycling the mixed gas of the N-methyl pyrrolidone carried out by a nitrogen flow and water into a recycling bottle A;
And (3) analyzing the mixed liquid A obtained in the recovery bottle A in real time, and judging the weight of the N-methylpyrrolidone and water in the mixed liquid A.
Further, the recovery bottle A is placed on a weighing mechanism, and a liquid level sensor is arranged in the recovery bottle A and comprises a processor; the processor is connected with the weighing mechanism and the liquid level sensor; and calculating the ratio of the N-methyl pyrrolidone to the water by utilizing the volume and the density of the mixed liquid A detected by the weighing mechanism and the liquid level sensor, and further calculating the weight of the N-methyl pyrrolidone to the water.
Further, in the step 3, the mixed gas of N-methylpyrrolidone and water carried out by the nitrogen flow is condensed and recovered into the recovery bottle B, the mixed liquid B obtained in the recovery bottle B is analyzed in real time, the weight of the N-methylpyrrolidone, the catalyst A and the water in the mixed liquid A is judged, the loss amount of the N-methylpyrrolidone in the first stage reaction process is judged, and the supplementing amount corresponding to the loss amount is added together in the second stage reaction initial stage.
Further, the catalyst A and the water are the addition amount of the catalyst A and the water content in a dehydration system respectively, the whole recovery bottle B is weighed by a weighing mechanism, and the loss amount of N-methylpyrrolidone is obtained after the catalyst A and the water are removed.
Further, the molar ratio of the catalyst A to the sodium sulfide pentahydrate is 0.15-0.25:1, a step of; the molar ratio of the catalyst B to the sodium sulfide pentahydrate is 0.15-0.25:1.
The invention has the following beneficial effects:
1. According to the invention, the lithium ion coated in the molecular chain in the polymerization reaction process is reduced as a whole by adopting different catalysts for catalysis in two stages of the polymerization reaction, so that the polyphenylene sulfide with low metal impurities is obtained.
2. In the invention, caprolactone is used as a catalyst in the first stage of the polymerization reaction, so that the 'wrapping' of lithium ions in the first stage is avoided when polyphenylene sulfide is formed; and simultaneously, after the first stage is finished, the temperature is kept for a period of time, caprolactone serving as a catalyst is evaporated and removed by utilizing high temperature, and lithium chloride is added subsequently to serve as a catalyst for catalytic reaction.
Of course, it is not necessary for any one product to practice the invention to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed for the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of the polyphenylene sulfide production method of the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, a method for producing polyphenylene sulfide with low metal impurities is provided, which comprises:
Step 1, adding sodium sulfide pentahydrate, sodium hydroxide and 3/5 of N-methyl pyrrolidone into a magnetic stirring reaction kettle, uniformly stirring, and keeping until the dehydration rate reaches 85-90% under the protection of nitrogen;
step 2, putting dichlorobenzene, caprolactone and 1/5 of N-methylpyrrolidone into a p-dichlorobenzene dissolving kettle, starting stirring, and heating the system to 70-150 ℃ under the protection of nitrogen until p-dichlorobenzene is dissolved in the N-methylpyrrolidone to obtain a solution A;
Step 3, adding the obtained solution A into the dehydration system obtained in the step 1, controlling the temperature to be raised to 180-190 ℃ and reacting at constant temperature for 240min to perform a first-stage reaction; heating to 225-235 ℃ for 15min, adding a solution B dissolved with lithium chloride, wherein the solution B is formed by dispersing lithium chloride into 1/5 dosage of N-methylpyrrolidone, and performing a second-stage reaction in a constant-temperature reaction mode for 300 min;
step 4, discharging after cooling according to a cooling program, filtering after discharging, washing a filter cake with deionized water, dehydrating and vacuum drying to obtain a product;
in the above, the molar ratio of caprolactone to sodium sulfide pentahydrate is 0.2:1, a step of; the molar ratio of the lithium chloride to the sodium sulfide pentahydrate used was 0.2:1.
Based on the experiment, the invention is carried out by adjusting the mole ratio of sodium sulfide pentahydrate and N-methyl pyrrolidone on the premise of keeping other conditions unchanged, and carries out related demonstration experiments, and the test results are shown in the following table one:
Table one: influence between the dehydration Rate of Na 2S·9H2 O and the addition amount of NMP as solvent
| Proportioning of | 2.5：1 | 3.0：1 | 3.2：1 | 3.5：1 | 4.0：1 |
| Test 1 | 84.26 | 86.17 | 87.50 | 87.2 | 89.65 |
| Test 2 | 80.65 | 84.27 | 90.48 | 90.76 | 85.89 |
| Test 3 | 87.25 | 87.61 | 88.44 | 88.25 | 94.8 |
| Average% | 84.1 | 86.27 | 88.8 | 88.73 | 90.1 |
| Standard deviation% | 2.70 | 1.37 | 1.24 | 1.49 | 3.65 |
Referring to Table one above, the dehydration rate was substantially between 86% and 91% and was relatively stable at a molar ratio of sodium sulfide pentahydrate to N-methylpyrrolidone in the range of 1:3.0-3.5.
Meanwhile, in the reaction control, when the reaction control is in the stage 1, the temperature is controlled to be raised to 210-215 ℃ and the temperature is kept constant for dehydration, when the dehydration rate reaches 65-75%, the heating is stopped, the dehydration system is utilized to complete secondary dehydration in a slow cooling process, the temperature is naturally lowered to 130-135 ℃, sampling detection is carried out to judge whether the dehydration rate reaches 85-90%, and if so, the reaction control is directly used; otherwise, starting a constant temperature system to keep the constant temperature treatment of the dehydration system within the range of 130-135 ℃ until the dehydration rate reaches 85-90% for standby.
Meanwhile, in the actual production process, because nitrogen is in a flowing state, a small amount of N-methylpyrrolidone is inevitably taken away in the process of volatilizing water, so in order to maintain the molar ratio of the N-methylpyrrolidone to sodium sulfide in a dehydration system, the N-methylpyrrolidone heated to 70-80 ℃ is added into a magnetic stirring reaction kettle in the step 1 while dehydration.
Of course, in order to determine the additional addition amount of N-methylpyrrolidone, the invention firstly measures N-methylpyrrolidone carried out by nitrogen flow to obtain the loss amount of N-methylpyrrolidone, and then supplements N-methylpyrrolidone corresponding to the loss amount into the magnetic stirring reaction kettle.
Specifically, condensing and recycling the mixed gas of N-methylpyrrolidone and water carried out by nitrogen flow into a recovery bottle A, analyzing the mixed liquid A obtained in the recovery bottle A in real time, and judging the weight of the N-methylpyrrolidone and the water in the mixed liquid A; the ratio of N-methylpyrrolidone to water in the mixed liquid A is calculated by detecting the density of the mixed liquid A, and the mass of N-methylpyrrolidone and water in the mixed liquid A are calculated respectively by utilizing the volume of the mixed liquid A, wherein the mass of N-methylpyrrolidone in the mixed liquid A is the loss of N-methylpyrrolidone.
It can be known that, in order to obtain the volume and the density of the mixed liquid A conveniently and obtain the mass of the N-methyl pyrrolidone and the water in the mixed liquid A technically, the recovery bottle A of the invention is placed on a weighing mechanism, and a liquid level sensor is arranged in the recovery bottle A and comprises a processor; the processor is connected with the weighing mechanism and the liquid level sensor; and calculating the ratio of the N-methyl pyrrolidone to the water by utilizing the volume and the density of the mixed liquid A detected by the weighing mechanism and the liquid level sensor, and further calculating the weight of the N-methyl pyrrolidone to the water.
As shown in table two below, the effect on dehydration was verified by the supplemental addition of N-methylpyrrolidone to the water as it was.
And (II) table: influence between the dehydration Rate of Na 2S·9H2 O and whether N-methylpyrrolidone was supplemented
As can be seen from the above table, the addition of supplemental N-methylpyrrolidone in real time according to the amount of N-methylpyrrolidone lost during the dehydration reaction is advantageous for improving the dehydration effect and the relative stability of the dehydration rate.
Of course, in the above, since caprolactone is easily volatilized at high temperature and overflows with nitrogen flow during polymerization, lithium chloride which does not volatilize is newly added as a catalyst to react after caprolactone is volatilized during use, and in step 3, the mixed gas of N-methylpyrrolidone and water carried out by the nitrogen flow is condensed and recovered into a recovery bottle B, the mixed liquid B obtained in the recovery bottle B is analyzed in real time, the weight of N-methylpyrrolidone, the catalyst A and water in the mixed liquid A is judged, the loss amount of N-methylpyrrolidone in the first stage reaction process is judged, and the supplementing amount corresponding to the loss amount is added together in the initial stage of the second stage reaction; specifically, the catalyst A and water are the addition amount of the catalyst A and the water content in a dehydration system respectively, the whole recovery bottle B is weighed by a weighing mechanism, and the loss amount of N-methylpyrrolidone is the removal amount of the catalyst A and the water.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, 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 present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (10)
1. A method for producing polyphenylene sulfide with low metal impurities, which is characterized by comprising the following steps:
Step 1, adding sodium sulfide pentahydrate, sodium hydroxide and N-methylpyrrolidone into a magnetic stirring reaction kettle, uniformly stirring, and keeping until the dehydration rate reaches 85-90% under the protection of nitrogen;
step 2, putting dichlorobenzene, a catalyst A and N-methylpyrrolidone into a p-dichlorobenzene dissolution kettle, starting stirring, and heating the system to 70-150 ℃ under the protection of nitrogen until the p-dichlorobenzene is dissolved in the N-methylpyrrolidone to obtain a solution A;
Step 3, adding the obtained solution A into the dehydration system obtained in the step 1, controlling the temperature to be raised to 180-190 ℃ and reacting at constant temperature for T1 time to perform a first-stage reaction; heating to 225-235 ℃ for T2, adding a solution B dissolved with a catalyst B, and performing a second-stage reaction in a constant-temperature reaction T3 time;
step 4, discharging after cooling according to a cooling program, filtering after discharging, washing a filter cake with deionized water, dehydrating and vacuum drying to obtain a product;
The catalyst A is caprolactam or caprolactone; the catalyst B is alkali metal acetate, lithium chloride, magnesium chloride, aluminum chloride, lithium benzoate, lithium stearate or lithium acetate.
2. The method for producing polyphenylene sulfide with low metal impurities according to claim 1, wherein the molar ratio of sodium sulfide pentahydrate to N-methylpyrrolidone in the step 1 is 1:3.0 to 3.5.
3. The method for producing polyphenylene sulfide with low metal impurities according to claim 1, wherein in the step 1, the temperature is raised to 210 ℃ to 215 ℃ for dehydration, when the dehydration rate reaches 65% to 75%, the temperature is naturally lowered to 130 ℃ to 135 ℃ and then the temperature is kept constant until the dehydration rate reaches 85% to 90% for standby.
4. The method for producing polyphenylene sulfide with low metal impurities according to claim 1, wherein in said step 1, N-methylpyrrolidone heated to 70 to 80 ℃ is additionally added to a magnetic stirring reaction vessel while dehydrating.
5. The method for producing polyphenylene sulfide with low metal impurities according to claim 4, wherein in said step 1, N-methylpyrrolidone loss is obtained by metering N-methylpyrrolidone carried out by nitrogen flow, and then N-methylpyrrolidone corresponding to the loss is added to the magnetic stirring reactor.
6. The method for producing polyphenylene sulfide with low metal impurities according to claim 5, wherein the method for calculating the loss amount of N-methylpyrrolidone comprises condensing a mixture of N-methylpyrrolidone and water carried out by a nitrogen stream and recycling the mixture into a recycling bottle A;
And (3) analyzing the mixed liquid A obtained in the recovery bottle A in real time, and judging the weight of the N-methylpyrrolidone and water in the mixed liquid A.
7. The method for producing polyphenylene sulfide with low metal impurities according to claim 6, wherein the recovery bottle a is placed on a weighing mechanism, and a liquid level sensor is provided in the recovery bottle a, and comprises a processor; the processor is connected with the weighing mechanism and the liquid level sensor; and calculating the ratio of the N-methyl pyrrolidone to the water by utilizing the volume and the density of the mixed liquid A detected by the weighing mechanism and the liquid level sensor, and further calculating the weight of the N-methyl pyrrolidone to the water.
8. The method for producing polyphenylene sulfide with low metal impurities according to claim 1, wherein in the step 3, a mixed gas of N-methylpyrrolidone and water carried out by a nitrogen stream is condensed and recovered into a recovery bottle B, and the mixed liquid B obtained in the recovery bottle B is analyzed in real time to determine the weight of N-methylpyrrolidone, the catalyst A and water in the mixed liquid A, and to determine the loss amount of N-methylpyrrolidone during the first-stage reaction, and to add a supplemental amount corresponding to the loss amount together in the initial stage of the second-stage reaction.
9. The method for producing polyphenylene sulfide with low metal impurities according to claim 8, wherein the catalyst a and water are the amount of catalyst a added and the water content in the dehydration system, respectively, the recovery bottle B is integrally weighed by a weighing mechanism, and the amount of loss of N-methylpyrrolidone is obtained by removing the catalyst a and the water.
10. The method for producing polyphenylene sulfide with low metal impurities according to claim 1, wherein the molar ratio of the catalyst a to the sodium sulfide pentahydrate is 0.15 to 0.25:1, a step of; the molar ratio of the catalyst B to the sodium sulfide pentahydrate is 0.15-0.25:1.
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