CN111471177A - Industrial production process and device of fiber-grade polyphenylene sulfide resin - Google Patents
Industrial production process and device of fiber-grade polyphenylene sulfide resin Download PDFInfo
- Publication number
- CN111471177A CN111471177A CN202010394347.4A CN202010394347A CN111471177A CN 111471177 A CN111471177 A CN 111471177A CN 202010394347 A CN202010394347 A CN 202010394347A CN 111471177 A CN111471177 A CN 111471177A
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- weight
- parts
- polyphenylene sulfide
- sulfide resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 46
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 36
- 229920005989 resin Polymers 0.000 title claims abstract description 36
- 238000009776 industrial production Methods 0.000 title description 6
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 54
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 239000000047 product Substances 0.000 claims abstract description 35
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000012216 screening Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 230000018044 dehydration Effects 0.000 claims description 10
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 9
- 239000001632 sodium acetate Substances 0.000 claims description 9
- 235000017281 sodium acetate Nutrition 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000011282 treatment Methods 0.000 claims description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 239000012066 reaction slurry Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000002131 composite material Substances 0.000 abstract description 5
- -1 organic acid salt Chemical class 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 150000001555 benzenes Chemical class 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 238000002411 thermogravimetry Methods 0.000 description 12
- 238000000113 differential scanning calorimetry Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000002798 polar solvent Substances 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
- 239000006227 byproduct Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000006902 nitrogenation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a production process of fiber-grade polyphenylene sulfide resin, which comprises the following steps: 1) adding acetic anhydride, sodium hydroxide and an organic solvent into a dehydration reaction kettle, reacting under the conditions of nitrogen protection and stirring, and then adding sodium hydrosulfide for reacting to obtain a sodium hydrosulfide solution; 2) transferring the sodium hydrosulfide solution into a polymerization reaction kettle, and adding dihalogenated benzene to carry out polymerization reaction; 3) and 5) cooling, screening, washing, filter-pressing and drying the obtained reaction mixed liquid to obtain a final product. According to the production process, sodium hydrosulfide and p-dichlorobenzene are adopted to synthesize the polyphenylene sulfide resin, so that the raw materials are low in price and easy to obtain, the yield is high, the product quality is stable, and the production process is suitable for industrial large-scale production. Compared with a composite catalytic system, the single organic acid salt catalytic system has the advantages of easy recovery of a solvent, low product cost, good safety, environmental protection and the like.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to an industrial production process of fiber-grade polyphenylene sulfide resin.
Background
Since the industrial production of polyphenylene sulfide resin by philips oil company in the united states began in the seventies of the twentieth century, the excellent chemical corrosion resistance, high temperature resistance, radiation resistance, high flame retardancy and the like of the engineering plastic have attracted more and more attention.
The main method for producing polyphenylene sulfide in the current industrial production comprises the following steps: a composite catalytic system is adopted to carry out solution polycondensation on sodium sulfide and dihalogenated aromatic compound at high temperature and high pressure. For example, in US33544129 philips produces polyphenylene sulfide by reacting sodium sulfide and p-dichlorobenzene under pressure in nitrogen in a polar solvent, n-methylpyrrolidone, but this process is energy intensive and costly. Chinese patent CN1143652A discloses a method for synthesizing tough polyphenylene sulfide resin by pressurizing sulfur as raw material in polar solvent, but the reaction process requires the use of reducing agent, the process is complex, the reaction by-products are more, and the product is not easy to purify. In the patent CN1793202A, sodium sulfide and p-dichlorobenzene are used as raw materials, and a composite catalytic system is used to synthesize a fiber-grade polyphenylene sulfide resin under pressure, but the catalyst used in the method is a composite catalytic system, and comprises a catalytic assistant and a catalyst, so that the product is difficult to purify, the catalyst is difficult to recover, the solvent recovery rate is low, and the production cost is high.
Therefore, there is still a need to develop a new more economical and environmentally friendly production process of polyphenylene sulfide.
Disclosure of Invention
In view of the problems of the prior art, according to one aspect of the present invention, it is an object of the present invention to provide a novel process for industrially producing a fiber-grade polyphenylene sulfide resin, in which an inexpensive organic acid salt is used as a catalyst to prepare polyphenylene sulfide, which is more economical and environmentally friendly, and in which the amount of residual catalyst in the product is very small, and no complicated post-treatment step is required. The production process of the invention is characterized in that sodium hydrosulfide and dihalogenated aromatic compound are used as raw materials, an organic acid salt single catalytic system is adopted in a polar solvent, and the high-performance fiber-grade polyphenylene sulfide resin is prepared by solution polycondensation reaction.
In order to achieve the above object of the present invention, the process for producing a pilot grade of the fiber-grade polyphenylene sulfide resin according to the present invention comprises the steps of:
1) adding 10-50 parts by weight of acetic anhydride, 100-200 parts by weight of sodium hydroxide and 300-600 parts by weight of organic solvent into a dehydration reaction kettle by a feed pump, gradually raising the temperature to 100-150 ℃ under the conditions of nitrogen protection and stirring, performing dehydration and acid-base neutralization reaction to generate sodium acetate, then adding 100-200 parts by weight of sodium hydrosulfide into the reaction kettle, and controlling the temperature at 200-210 ℃ to perform dehydration reaction for 1.5-3 h to obtain a dehydrated sodium hydrosulfide solution;
2) transferring the sodium hydrosulfide solution from the dehydration reaction kettle to a subsequent polymerization reaction kettle, adding 200 parts by weight of dihalobenzene into the dehydration reaction kettle, heating the polymerization reaction kettle to 265-280 ℃, keeping the stirring condition for 0.5h for polymerization reaction, then cooling the polymerization reaction kettle to below 100 ℃ under the condition of keeping the pressure in the reactor unchanged, and finishing the reaction;
3) cooling and screening the reaction mixed liquid obtained in the step 2);
4) washing and filter-pressing the reaction product screened in the step 3) for multiple times by deionized water;
5) and (3) drying the reaction product obtained in the step 3) in an oven at the temperature of 120-130 ℃ for more than 3h to obtain the polyphenylene sulfide resin.
Preferably, the organic solvent in step 1) is Nitrogen Methyl Pyrrolidone (NMP).
Preferably, the amount of the acetic anhydride used in step 1) is 20 to 40 parts by weight.
Preferably, the amount of the sodium hydroxide used in the step 1) is 120-180 parts by weight.
Preferably, the amount of the organic solvent used in step 1) is 400-500 parts by weight.
Preferably, the amount of the sodium hydrosulfide used in the step 1) is 150-200 parts by weight.
Further preferably, the amount of the acetic anhydride used in step 1) is 20 to 30 parts by weight.
Further preferably, the amount of the sodium hydroxide used in step 1) is 140-150 parts by weight.
Further preferably, the amount of the organic solvent used in step 1) is 440-460 parts by weight.
Further preferably, the amount of the sodium hydrosulfide used in the step 1) is 170-180 parts by weight.
Preferably, the dihalobenzene in step 2) is p-dichlorobenzene.
Preferably, the dihalobenzene is used in an amount of 150-200 parts by weight in step 2).
Further preferably, the dihalobenzene is used in an amount of 190-200 parts by weight in the step 2).
According to another aspect of the present invention, it is another object of the present invention to provide a production apparatus of the production process of fiber-grade polyphenylene sulfide resin, the apparatus comprising:
the dehydration reaction kettle is used for performing dehydration reaction, an oil bath heating sleeve is wrapped outside the dehydration reaction kettle for heating, a stirrer is arranged inside the dehydration reaction kettle, and an air outlet is formed in the top of the dehydration reaction kettle and used for evaporating water and a small amount of solvent N-methyl pyrrolidone and hydrogen sulfide from the top;
the polymerization reaction kettle is used for carrying out polymerization reaction and receiving a product from the dehydration reaction kettle and p-dichlorobenzene as reactants, an oil bath heating sleeve is wrapped outside the polymerization reaction kettle for heating, a stirrer is arranged inside the polymerization reaction kettle, and a discharge pipeline is arranged at the bottom of the polymerization reaction kettle and used for conveying reaction slurry to a subsequent screening and washing system;
and the condensation tank is connected with a gas outlet at the top of the polymerization reaction kettle and is used for receiving gases such as water vapor, nitrogen and the like from the dehydration reaction kettle and the polymerization reaction kettle so as to condense.
Preferably, the product of the dehydration reaction kettle is directly introduced into the polymerization reaction kettle without other treatment.
Advantageous effects
1. The invention adopts sodium hydrosulfide and dihalogenated aromatic compound (p-dichlorobenzene) to synthesize the polyphenylene sulfide resin, has cheap and easily obtained raw materials, higher yield and stable product quality, and is suitable for industrialized large-scale production.
2. The production process adopts a single organic acid salt catalytic system, and compared with a composite catalytic system, the organic acid salt catalytic system has the advantages of easy recovery of a solvent, low product cost, good safety, environmental protection and the like.
3. The polyphenylene sulfide synthesized by the method has the advantages of high melting point, easy processing and high temperature resistance.
4. The production process of the invention has simple operation, easy control of reaction conditions, good repeatability and reasonable energy consumption.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a block flow diagram of the process for producing the fiber-grade polyphenylene sulfide resin according to the present invention;
FIG. 2 is a schematic structural view of a production apparatus of the process for producing a fiber-grade polyphenylene sulfide resin according to the present invention;
FIG. 3 is a DSC analysis chart of the product of example 1
FIG. 4 is a TGA analysis of the product of example 1
FIG. 5 is a DSC analysis chart of the product of example 2
FIG. 6 is a TGA analysis of the product of example 2
FIG. 7 is a DSC analysis chart of the product of example 3
FIG. 8 is a TGA analysis of the product of example 3
FIG. 9 is a DSC analysis chart of the product of example 4
FIG. 10 is a TGA analysis of the product of example 4
FIG. 11 is a DSC analysis of the product of example 5
FIG. 12 is a TGA analysis of the product of example 5
Detailed Description
Hereinafter, preferred embodiments of the present disclosure will be described in detail with reference to the accompanying drawings. Before the description, it should be understood that the terms used in the specification and the appended claims should not be construed as limited to general and dictionary meanings, but interpreted based on the meanings and concepts corresponding to technical aspects of the present invention on the basis of the principle that the inventor is allowed to define terms appropriately for the best explanation. Accordingly, the description herein of preferred embodiments is for the purpose of illustration only and is not intended to limit the scope of the invention, so it will be understood that other equivalent implementations and modifications may be made without departing from the spirit and scope of the invention.
In order to clarify the present invention, portions irrelevant to the description are omitted in the drawings, and the same or similar components are denoted by the same reference numerals throughout the specification.
In addition, the size and thickness of each component shown in the drawings are arbitrarily illustrated for convenience of explanation, and thus the present invention is not necessarily limited to those illustrated in the drawings.
Throughout the specification, when an element is referred to as being "connected" to another element, it includes not only "direct connection" but also "indirect connection" between other members. In addition, when an element is referred to as "comprising" a component, it means that the element may further comprise other components rather than excluding other components, unless expressly stated to the contrary.
The pilot scale production process of the fiber-grade polyphenylene sulfide resin according to the present invention comprises the steps of:
1) adding 10-50 parts by weight of acetic anhydride, 100-200 parts by weight of sodium hydroxide and 300-600 parts by weight of organic solvent into a dehydration reaction kettle by a feed pump, gradually increasing the temperature to 100-150 ℃ under the conditions of nitrogen protection and stirring, performing dehydration and acid-base neutralization reaction to generate sodium acetate, then adding 100-200 parts by weight of sodium hydrosulfide into the reaction kettle, and controlling the temperature at 200-210 ℃ to perform dehydration reaction for 1.5-3 h to obtain a dehydrated sodium hydrosulfide solution;
2) transferring the sodium hydrosulfide solution from the dehydration reaction kettle to a subsequent polymerization reaction kettle, adding 200 parts by weight of dihalobenzene into the dehydration reaction kettle, heating the polymerization reaction kettle to 265-280 ℃, keeping the stirring condition for 0.5h for polymerization reaction, then cooling the polymerization reaction kettle to below 100 ℃ under the condition of keeping the pressure in the reactor unchanged, and finishing the reaction;
3) cooling and screening the reaction mixed liquid obtained in the step 2);
4) washing and filter-pressing the reaction product screened in the step 3) for multiple times by deionized water;
5) and (3) drying the reaction product obtained in the step 3) in an oven at the temperature of 120-130 ℃ for more than 3h to obtain the polyphenylene sulfide resin.
Among them, the amount of the acetic anhydride used in the step 1) is preferably 20 to 40 parts by weight, more preferably 20 to 30 parts by weight.
Preferably, the amount of the sodium hydroxide used in step 1) is 120-180 parts by weight, more preferably 140-150 parts by weight.
Preferably, the amount of the organic solvent used in step 1) is 400-500 parts by weight, more preferably 440-460 parts by weight.
Preferably, the amount of the sodium hydrosulfide used in the step 1) is 150-200 parts by weight, more preferably 170-180 parts by weight.
When the amount of the above-mentioned reactants is controlled within the above range, optimal reaction efficiency can be achieved and the content of impurities in the product can be minimized. It can be seen that the ratio of the amount of sodium hydroxide to the amount of acetic anhydride is higher than the molar atomic ratio of sodium acetate. If the sodium hydroxide is insufficient, the subsequent reaction can not be smoothly carried out; if the consumption of acetic anhydride is too large, the product has too many impurities, and the subsequent washing and other treatments are complicated, so that the cost is increased.
Likewise, in order to optimize the reaction, it is preferable that the dihalobenzene is used in an amount of 150-200 parts by weight, more preferably 190-200 parts by weight in step 2). When the amount is within this range, the polymerization reaction is most economical, and the reaction efficiency is lowered by using an excessive or insufficient amount of dihalobenzene.
Preferably, after the polymerization reaction at the temperature of 265 ℃ and 280 ℃ is completed in the step 2), the temperature is reduced under the condition of keeping the pressure in the reactor unchanged, the temperature of the reaction kettle is reduced from the reaction temperature to 240 ℃ to 230 ℃ within 40 to 55 minutes according to a strict temperature reduction curve, then the temperature is reduced from 230 ℃ to below 100 ℃ within 160 to 200 minutes, product particles are separated out, and the obtained product polyphenylene sulfide is a fiber-grade product and is granular.
The industrial production process of the fiber-grade polyphenylene sulfide resin has the design capacity of producing 80 tons of polyphenylene sulfide products per year, and the reaction cycle time is 12 hours. The capacities of the dehydration reaction kettle and the polymerization reaction kettle are both 1.5m3. In the dehydration reactor, water and a small amount of solvent N-methylpyrrolidone and hydrogen sulfide are distilled out from the top. The nitrogen used as the nitrogen seal is discharged from the top of the reactor in the process of filling raw materials into the reaction kettle, and the dehydrated raw materials are transferred to a subsequent polymerization reaction kettle. In the polymerization reactor, the polymerization product is cooled, and polyphenylene sulfide powder and byproduct salt are crystallized together. After crystallization, the reaction slurry in the whole reaction kettle is sent to a subsequent screening and washing system.
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, and it will be understood by those skilled in the art that modifications may be made without departing from the spirit and scope of the invention. Unless otherwise specified, reagents and equipment used in the following examples are commercially available products.
The performance tests of various substances were carried out as follows, all according to methods conventional in the art:
1. polyphenylene sulfide with different melt flow rates is prepared by regulating and controlling the concentration of reactants, the material ratio and the reaction temperature, and the melt index of the polyphenylene sulfide is measured by a melt index meter (the temperature is 316 ℃, and the load is 5 kg).
2. The melting point of the polyphenylene sulfide resin was measured by Differential Scanning Calorimetry (DSC).
3. The polyphenylene sulfide resin was tested for heat weight loss using the thermogravimetric analysis method (TGA).
4. The ash content of the polyphenylene sulfide resin was measured by a muffle furnace combustion method.
5. And testing the volatility of the polyphenylene sulfide resin by adopting a heating decrement method.
The kind and purity of the starting materials are as follows:
| species of | Purity of |
| Sodium hydrosulfide | 43.12％ |
| P-dichlorobenzene | 99.99％ |
| N-methyl pyrrolidone | 99.86％ |
| Sodium hydroxide | 49.97％ |
| Acetic anhydride | 99.34％ |
Example 1
20kg of acetic anhydride, 140kg of sodium hydroxide and 440kg of organic solvent are added into a dehydration reaction kettle, the temperature is gradually raised to 100-150 ℃ under the protection of nitrogen, and dehydration and acid-base neutralization reaction are carried out to generate sodium acetate. And adding 170kg of sodium hydrosulfide into the reaction kettle, and raising the temperature to 200-210 ℃ for dehydration reaction for 2h to obtain a dehydrated solution. Transferring the solution from the dehydration reaction kettle to a subsequent polymerization reaction kettle, adding 195kg of p-dichlorobenzene, heating the medium in the reaction kettle to 265-280 ℃, then keeping the temperature at 265-280 ℃ for 1h, and cooling to below 100 ℃. And screening the reaction mixed solution, washing and filter-pressing the screened reaction product for multiple times by using deionized water, and drying for 3 hours in an oven at the temperature of 120-130 ℃ to obtain the polyphenylene sulfide resin.
The product obtained was in the form of granules having a particle size of about 5 to 15mm, a yield of 92.39% and a melt index of 290g/10min (measured according to the national standard GB/T3682-2000). DSC analysis is shown in FIG. 2: the melting point is 284.8 ℃. Thermogravimetric analysis is shown in fig. 3: the weight loss on heating at 300 ℃ was 0.27%. The ash content at 550 ℃ is 0.39% (measured according to the national standard GB/T9345.1-2008). The volatility at 150 ℃ was 0.32%. Has better thermal performance.
Example 2
Adding 22kg of acetic anhydride, 144kg of sodium hydroxide and 442kg of organic solvent into a dehydration reaction kettle, gradually raising the temperature to 100-150 ℃ under the protection of nitrogen, and carrying out dehydration and acid-base neutralization reaction to generate sodium acetate. And adding 174kg of sodium hydrosulfide into the reaction kettle, and raising the temperature to 200 ℃ and 210 ℃ for dehydration reaction for 2 hours to obtain a dehydrated solution. Transferring the solution from the dehydration reaction kettle to a subsequent polymerization reaction kettle, adding 195kg of p-dichlorobenzene, heating the medium in the reaction kettle to 265-280 ℃, then keeping the temperature at 265-280 ℃ for 0.5h, and cooling to below 100 ℃. And screening the reaction mixed solution, washing and filter-pressing the screened reaction product for multiple times by using deionized water, and drying for 3 hours in an oven at the temperature of 120-130 ℃ to obtain the polyphenylene sulfide resin.
The product obtained was in the form of granules having a particle size of about 5 to 15mm, a yield of 93.42% and a melt index of 201g/10min (measured according to the national standard GB/T3682-2000). DSC analysis is shown in FIG. 4: its melting point was 284.7 ℃. Thermogravimetric analysis is shown in fig. 5: the heating weight loss at 300 ℃ was 0.25%. An ash content of 0.35% at 550 ℃ (measured according to the national standard GB/T9345.1-2008). The volatility at 150 ℃ was 0.25%. Has better thermal performance.
Example 3
Adding 24kg of acetic anhydride, 146kg of sodium hydroxide and 450kg of organic solvent into a dehydration reaction kettle, gradually raising the temperature to 100-150 ℃ under the protection of nitrogen, and carrying out dehydration and acid-base neutralization reaction to generate sodium acetate. And adding 176kg of sodium hydrosulfide into the reaction kettle, and raising the temperature to 200 ℃ and 210 ℃ for dehydration reaction for 2 hours to obtain a dehydrated solution. Transferring the solution from the dehydration reaction kettle to a subsequent polymerization reaction kettle, adding 198kg of p-dichlorobenzene, heating the medium in the reaction kettle to 265-280 ℃, then keeping the temperature at 265-280 ℃ for 0.5h, and cooling to below 100 ℃. And screening the reaction mixed solution, washing and filter-pressing the screened reaction product for multiple times by using deionized water, and drying for 3 hours in an oven at the temperature of 120-130 ℃ to obtain the polyphenylene sulfide resin.
The product obtained was in the form of granules having a particle size of about 5 to 15mm, a yield of 92.39% and a melt index of 172g/10min (measured according to the national standard GB/T3682-2000). DSC analysis is shown in FIG. 6: its melting point was 286.2 ℃. Thermogravimetric analysis is shown in fig. 7: the heating weight loss at 300 ℃ was 0.25%. An ash content of 0.26% at 550 ℃ (measured according to the national standard GB/T9345.1-2008). The volatility at 150 ℃ is 0.36%. Has better thermal performance.
Example 4
Adding 26kg of acetic anhydride, 148kg of sodium hydroxide and 455kg of organic solvent into a dehydration reaction kettle, gradually raising the temperature to 100-150 ℃ under the protection of nitrogen, and carrying out dehydration and acid-base neutralization reaction to generate sodium acetate. 178kg of sodium hydrosulfide is added into the reaction kettle, the temperature is raised to 200 ℃ and 210 ℃ for dehydration reaction for 2h, and the dehydrated solution is obtained. Transferring the solution from the dehydration reaction kettle to a subsequent polymerization reaction kettle, adding 198kg of p-dichlorobenzene, heating the medium in the reaction kettle to 265-280 ℃, then keeping the temperature at 265-280 ℃ for 1h, and cooling to below 100 ℃. And screening the reaction mixed solution, washing and filter-pressing the screened reaction product for multiple times by using deionized water, and drying for 3 hours in an oven at the temperature of 120-130 ℃ to obtain the polyphenylene sulfide resin.
The product obtained was in the form of granules having a particle size of about 5 to 15mm, a yield of 92.39% and a melt index of 173g/10min (measured according to the national standard GB/T3682-2000). DSC analysis is shown in FIG. 8: its melting point was 286.2 ℃. Thermogravimetric analysis is shown in fig. 9: the heating weight loss at 300 ℃ was 0.26%. The ash content at 550 ℃ is 0.29% (measured according to the national standard GB/T9345.1-2008). The volatility at 150 ℃ was 0.32%. Has better thermal performance.
Example 5
Adding 28kg of acetic anhydride, 150kg of sodium hydroxide and 460kg of organic solvent into a dehydration reaction kettle, and gradually raising the temperature under the protection of nitrogen to perform dehydration and acid-base neutralization reaction to generate sodium acetate. And adding 180 parts of sodium hydrosulfide into the reaction kettle, and raising the temperature to 200-210 ℃ for dehydration reaction for 2 hours to obtain a dehydrated solution. Transferring the solution from the dehydration reaction kettle to a subsequent polymerization reaction kettle, adding 200kg of p-dichlorobenzene, heating the medium in the reaction kettle to 265-280 ℃, then keeping the temperature at 265-280 ℃ for 0.5h, and cooling to below 100 ℃. And screening the reaction mixed solution, washing and filter-pressing the screened reaction product for multiple times by using deionized water, and drying for 3 hours in an oven at the temperature of 120-130 ℃ to obtain the polyphenylene sulfide resin.
The product obtained was in the form of granules having a particle size of about 5 to 15mm, a yield of 92.39% and a melt index of 380g/10min (measured according to the national standard GB/T3682-2000). DSC analysis is shown in FIG. 10: its melting point was 286.0 ℃. Thermogravimetric analysis is shown in fig. 11: the weight loss on heating at 300 ℃ was 0.18%. Ash at 550 ℃ was 0.24% (measured according to national standard GB/T9345.1-2008). The volatility at 150 ℃ is 0.28%. Has better thermal performance.
The existing documents, such as the technologies disclosed in chinese patents CN1143652A and CN1793202A, are laboratory-level technologies, and cannot be scaled up to realize actual production on an industrial scale. The embodiment proves that the production process can realize high-efficiency production in an industrial scale level, and simultaneously, because the raw materials are cheap and easy to obtain, the process flow design is simple, and conventional inorganic salts such as lithium chloride and the like are not adopted as catalysts, the practical problems that the product is difficult to purify, the catalyst is difficult to recover, the solvent recovery rate is low, the production cost is high and the like are solved.
Claims (8)
1. A production process of fiber-grade polyphenylene sulfide resin comprises the following steps:
1) adding 10-50 parts by weight of acetic anhydride, 100-200 parts by weight of sodium hydroxide and 300-600 parts by weight of organic solvent into a dehydration reaction kettle by a feed pump, gradually raising the temperature to 100-150 ℃ under the conditions of nitrogen protection and stirring, performing dehydration and acid-base neutralization reaction to generate sodium acetate, then adding 100-200 parts by weight of sodium hydrosulfide into the reaction kettle, and controlling the temperature at 200-210 ℃ to perform dehydration reaction for 1.5-3 h to obtain a dehydrated sodium hydrosulfide solution;
2) transferring the sodium hydrosulfide solution from the dehydration reaction kettle to a subsequent polymerization reaction kettle, adding 200 parts by weight of dihalobenzene into the dehydration reaction kettle, heating the polymerization reaction kettle to 265-280 ℃, keeping the stirring condition for 0.5h for polymerization reaction, then cooling the polymerization reaction kettle to below 100 ℃ under the condition of keeping the pressure in the reactor unchanged, and finishing the reaction;
3) cooling and screening the reaction mixed liquid obtained in the step 2);
4) washing and filter-pressing the reaction product screened in the step 3) for multiple times by deionized water;
5) and (3) drying the reaction product obtained in the step 3) in an oven at the temperature of 120-130 ℃ for more than 3h to obtain the polyphenylene sulfide resin.
2. The process for producing fiber-grade polyphenylene sulfide resin according to claim 1, wherein the organic solvent in step 1) is N-methyl pyrrolidone (NMP), and the amount of the organic solvent is preferably 400-500 parts by weight, more preferably 440-460 parts by weight.
3. The process for producing fiber-grade polyphenylene sulfide resin according to claim 1, wherein the amount of acetic anhydride used in step 1) is 20 to 40 parts by weight, more preferably 20 to 30 parts by weight.
4. The process for producing fiber-grade polyphenylene sulfide resin according to claim 1, wherein the amount of sodium hydroxide used in step 1) is 120-180 parts by weight, more preferably 140-150 parts by weight.
5. The process for producing fiber-grade polyphenylene sulfide resin according to claim 1, wherein the amount of sodium hydrosulfide in step 1) is 150-200 parts by weight, more preferably 170-180 parts by weight.
6. The process for producing fiber-grade polyphenylene sulfide resin according to claim 1, wherein the dihalobenzene is p-dichlorobenzene in step 2), and the amount of the dihalobenzene in step 2) is preferably 150-200 parts by weight, more preferably 190-200 parts by weight.
7. A production apparatus of the production process of fiber-grade polyphenylene sulfide resin according to claims 1 to 6, comprising:
the dehydration reaction kettle is used for performing dehydration reaction, an oil bath heating sleeve is wrapped outside the dehydration reaction kettle for heating, a stirrer is arranged inside the dehydration reaction kettle, and an air outlet is formed in the top of the dehydration reaction kettle and used for evaporating water and a small amount of solvent N-methyl pyrrolidone and hydrogen sulfide from the top;
the polymerization reaction kettle is used for carrying out polymerization reaction and receiving a product from the dehydration reaction kettle and p-dichlorobenzene as reactants, an oil bath heating sleeve is wrapped outside the polymerization reaction kettle for heating, a stirrer is arranged inside the polymerization reaction kettle, and a discharge pipeline is arranged at the bottom of the polymerization reaction kettle and used for conveying reaction slurry to a subsequent screening and washing system;
and the condensation tank is connected with a gas outlet at the top of the polymerization reaction kettle and is used for receiving gases such as water vapor, nitrogen and the like from the dehydration reaction kettle and the polymerization reaction kettle so as to condense.
8. The production apparatus as claimed in claim 7, wherein the product of the dehydration reactor is directly introduced into the polymerization reactor without further treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010394347.4A CN111471177A (en) | 2020-05-11 | 2020-05-11 | Industrial production process and device of fiber-grade polyphenylene sulfide resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010394347.4A CN111471177A (en) | 2020-05-11 | 2020-05-11 | Industrial production process and device of fiber-grade polyphenylene sulfide resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111471177A true CN111471177A (en) | 2020-07-31 |
Family
ID=71764458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010394347.4A Pending CN111471177A (en) | 2020-05-11 | 2020-05-11 | Industrial production process and device of fiber-grade polyphenylene sulfide resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111471177A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0374719A2 (en) * | 1988-12-13 | 1990-06-27 | Phillips Petroleum Company | Higher molecular weight arylene sulfide resin and process for its preparation |
| CN101139280A (en) * | 2007-10-11 | 2008-03-12 | 宋桂兰 | Sodium acetate anhydrous and preparation method and usage thereof |
| CN103087523A (en) * | 2012-12-26 | 2013-05-08 | 四川大学 | Extrusion-grade polyarylene sulfide bar and preparation method thereof |
| CN103467741A (en) * | 2013-09-22 | 2013-12-25 | 四川大学 | Polyphenylene sulfide and preparation method thereof |
| CN103709405A (en) * | 2013-12-16 | 2014-04-09 | 四川大学 | High-purity autocatalytic polyarylene sulfide and preparation method thereof |
| CN103923317A (en) * | 2014-05-05 | 2014-07-16 | 重庆海洲化学品有限公司 | Application of sodium acetate as catalyst for preparing polyphenylene sulfide and method for preparing polyphenylene sulfide |
| CN106893102A (en) * | 2017-03-10 | 2017-06-27 | 四川中科兴业高新材料有限公司 | A kind of method that synthesis mother liquid prepares polyphenylene sulfide |
| CN109535426A (en) * | 2018-11-27 | 2019-03-29 | 德阳科吉高新材料有限责任公司 | A kind of polyphenylene sulfide synthesis technology |
| CN110072917A (en) * | 2017-05-15 | 2019-07-30 | 株式会社Lg化学 | The method for being used to prepare poly arylidene thio-ester |
-
2020
- 2020-05-11 CN CN202010394347.4A patent/CN111471177A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0374719A2 (en) * | 1988-12-13 | 1990-06-27 | Phillips Petroleum Company | Higher molecular weight arylene sulfide resin and process for its preparation |
| CN101139280A (en) * | 2007-10-11 | 2008-03-12 | 宋桂兰 | Sodium acetate anhydrous and preparation method and usage thereof |
| CN103087523A (en) * | 2012-12-26 | 2013-05-08 | 四川大学 | Extrusion-grade polyarylene sulfide bar and preparation method thereof |
| CN103467741A (en) * | 2013-09-22 | 2013-12-25 | 四川大学 | Polyphenylene sulfide and preparation method thereof |
| CN103709405A (en) * | 2013-12-16 | 2014-04-09 | 四川大学 | High-purity autocatalytic polyarylene sulfide and preparation method thereof |
| CN103923317A (en) * | 2014-05-05 | 2014-07-16 | 重庆海洲化学品有限公司 | Application of sodium acetate as catalyst for preparing polyphenylene sulfide and method for preparing polyphenylene sulfide |
| CN106893102A (en) * | 2017-03-10 | 2017-06-27 | 四川中科兴业高新材料有限公司 | A kind of method that synthesis mother liquid prepares polyphenylene sulfide |
| CN110072917A (en) * | 2017-05-15 | 2019-07-30 | 株式会社Lg化学 | The method for being used to prepare poly arylidene thio-ester |
| CN109535426A (en) * | 2018-11-27 | 2019-03-29 | 德阳科吉高新材料有限责任公司 | A kind of polyphenylene sulfide synthesis technology |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109092309B (en) | Preparation method of catalyst for preparing 5-hydroxymethylfurfural from cellulose | |
| CN102153494A (en) | Synthesis technology for N,N-diethylamino group ethanethiol | |
| CN105621398A (en) | Method for preparing high-purity graphite fluoride by catalytic method | |
| CN1027809C (en) | Method for synthesizing paraffin chloride | |
| CN114380965B (en) | Polybenzimidazole ionic covalent organic framework material BM-S and preparation method and application thereof | |
| CN110294844B (en) | Method for synthesizing high molecular weight polyphenylene sulfide by controlling water content | |
| CN117986162B (en) | Preparation method of ethyl sulfonyl chloride | |
| CN115260496A (en) | Process for producing polyarylene sulfide resin, product thereof and use thereof | |
| CN101003466A (en) | Method for synthesizing bisphenol fluorine by catalysis of highly acidic cation exchange resin | |
| CN113120925B (en) | Method for recovering iodide from isophorone cracking material | |
| CN109535425A (en) | A kind of polyphenylene sulfide resin production process | |
| CN107254047B (en) | Method for preparing polyphenylene sulfide by condensation polymerization of p-dichlorobenzene | |
| CN111471177A (en) | Industrial production process and device of fiber-grade polyphenylene sulfide resin | |
| CN103708518B (en) | Anhydrous aluminum chloride preparation method | |
| CN110272546B (en) | Method for synthesizing polyether sulfone resin | |
| CN114085189A (en) | Preparation method and application of metal-diimidazole salt ionic liquid catalyst | |
| CN111533910A (en) | Industrial production process and device of injection molding polyphenylene sulfide resin | |
| CN115228111B (en) | Device and method for preparing hydrogen sulfide through reactive distillation | |
| CN110066261B (en) | Energy-saving water-saving environment-friendly method for preparing furfural | |
| CN117229178A (en) | Method for preparing clt acid by liquid phase baking method | |
| CN110372520B (en) | Catalytic synthesis method of p-n-butylaniline | |
| CN103242879A (en) | Production method of modified pitch | |
| CN114163299B (en) | Production system and method for co-production of polyvinyl chloride by coal-based ethylene method and calcium carbide acetylene method | |
| CN114437338B (en) | Synthesis method of polyether-ether-ketone | |
| CN115466204B (en) | Continuous production method of 2, 2-dimethyl thiopropane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200731 |
|
| RJ01 | Rejection of invention patent application after publication |