CN109535426A - A kind of polyphenylene sulfide synthesis technology - Google Patents
A kind of polyphenylene sulfide synthesis technology Download PDFInfo
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- CN109535426A CN109535426A CN201811427061.0A CN201811427061A CN109535426A CN 109535426 A CN109535426 A CN 109535426A CN 201811427061 A CN201811427061 A CN 201811427061A CN 109535426 A CN109535426 A CN 109535426A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
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Abstract
The invention discloses a kind of polyphenylene sulfide synthesis technologies, purpose is that obtain a kind of grain forming good, product yield is high, solvent recovering rate is high, the resin syntheses processes that polymerizing reactor extent of corrosion reduces, the present invention uses the NaHS containing the crystallization water, sodium hydroxide, paracide is raw material, N-Methyl pyrrolidone is solvent, condensation polymerization reaction occurs in synthetic system, after the completion of low temperature and high-temperature polycondensation, acetate is added with high-pressure pump, NMP and aqueous solution, through soak after it, cooling, filtering, filter cake through nmp solvent after purification, it is washed repeatedly with deionized water again, filtering, filtration cakes torrefaction, polyphenylene sulfide is made, the polyphenylene sulfide that the present invention synthesizes, it is widely used in space flight and aviation, electric mechanical, petrochemical industry, food, light industry, thermal power generation, cement industry , steel and iron manufacturing, environmental protection, the fields such as textile industry.
Description
Technical field
The present invention relates to a kind of synthesis field of resin material, in particular to a kind of synthesis technology of polyphenylene sulfide.
Background technique
Linear high molecular weight polyphenylene sulfide (PPS), with good chemical property and physical property, is widely answered with it
Used in space flight and aviation electric mechanical, the industrial technical fields such as petrochemical industry, food, light industry, synthesis technology is increasingly by the world
The attention of various countries.United States Patent (USP) US4910294, European patent EP 0256757, United States Patent (USP) US4794164 describe two steps
Method synthesizes the technique of PPS, but the method for being all not directed to charging.Industrial synthetic process of the country about PPS, rarely seen Chinese patent
The synthesis technology and its process regulation method that CN971073570 is announced, one is nearly all used during polymerization reaction
Secondary property charging process, this method is in charging, it is necessary to and temperature in the kettle is reduced to 160 DEG C and is fed hereinafter, opening kettle again, otherwise,
One of the material of PPS polymerization reaction is participated in, material proportion changes caused by paracide p-DCB can escape because of vaporization, after charging again
Again heating is reacted, and not only influences reaction success rate, but also energy consumption is high, the exothermic reaction that PPS is synthetically produced makes to have in kettle
Vaporized material generates, and increases reactor pressure, in order to guarantee that PPS can be synthesized under normal pressure, often exhaust pressure relief,
But a possibility that exhaust will take away partial material simultaneously, keep material proportion unbalance, lead to reaction failure or molecular weight very little.
Introduce in Chinese patent application CN001161407 and 201110066322.2 a kind of synthesis polyphenylene sulfide
Process control condition, wherein not excessive elaboration polyphenylene sulfide closes other than several conventional temperature, pressure parameters
At technology controlling and process index.
The polyphenyl using the additive synthesis after a kind of processing synthesis of reducing agent is described in United States Patent (USP) NO:4820101
Sulfide resin, to reduce the content of the chlorine element in polyphenylene sulfide, by treated in this way, polyphenylene sulfide is made
For electronic package material, the purpose is to improve the electrical insulation capability of electronic apparatus material, which is also by the way of sealing end
The polyphenylene sulfide of low molecular weight is handled, but the price of this reducing compound is relatively high, to increase synthesis
The cost of polyphenylene sulfide.
Described in Chinese patent application 201610033529.2 it is a kind of use sodium acetate for synthesize polyphenylene sulfide
Cosolvent, due to being influenced by sodium acetate crystal shape after polyphenylene sulfide synthesizes so that polyphenylene sulfide at
Type is relatively difficult.
A kind of polyphenylene sulfide for not adding any auxiliary agent is described in Chinese patent application 201410087155.3
Industrial synthetic process uses NaHS and sodium hydroxide and paracide for raw material, with N- methyl -2- pyrroles wherein
Alkanone is solvent, and polycondensation synthesizes polyphenylene sulfide under conditions of not adding any additive synthesis, due to by polymerization reaction body
The influence of series solvent amount, so that the polyphenylene sulfide particle after synthesis is very irregular, while there is also polyphenylene sulfides
Particle is very tiny, is unfavorable for the purifying and washing in later period.
A kind of polyphenylene sulfide for not adding any additive synthesis is described in Chinese patent application 201410087185.4
The industrial synthetic process NaHS and sodium hydroxide and paracide of resin are raw material, N-Methyl pyrrolidone (referred to as: NMP)
For solvent, polycondensation synthesizes polyphenylene sulfide under conditions of not adding any additive synthesis, in the synthesis process, due to system
Solvent content it is relatively fewer so that the viscosity of polymerization reaction system is relatively high, after completion of the polymerization reaction, be unfavorable for polymerizeing
The cooling of reaction system.
Summary of the invention
The object of the present invention is to provide a kind of polyphenylene sulfide synthesis technologies, it is therefore an objective to obtain a kind of grain forming it is good,
The resin syntheses processes that product yield is high, solvent recovering rate is high, polymerizing reactor extent of corrosion reduces.
The present invention is realized by following technique:
A kind of polyphenylene sulfide synthesis technology, use the NaHS containing certain crystallization water, sodium hydroxide, paracide for
Raw material, N-Methyl pyrrolidone are solvent to synthesize polyphenylene sulfide, before dewatering process process starts, need be dehydrated
It is separately added into NaHS, sodium hydroxide in the differential responses kettle of system, and is configured to the aqueous solution of certain mass concentration respectively,
Reaction kettle is heated respectively simultaneously, under conditions of temperature rise to certain temperature, two aqueous solutions are mixed, and keeps the temperature one
It fixes time after generating vulcanized sodium, nmp solvent is added, heating dehydration is carried out to dewatering system immediately, after being dehydrated completion,
The vulcanized sodium that paracide generates is added in synthetic system, condensation polymerization reaction occurs, after the completion of low temperature and high-temperature polycondensation, uses
Acetate, NMP and aqueous solution is added in high-pressure pump, and thereafter, polymerization system temperature is after 260~270 DEG C of held for some time, polymerization
Reaction system is cooled to 160~180 DEG C, filters while hot, and filter cake after purification, then with deionized water carries out instead it through nmp solvent
After backwashing is washed, filtering, and polyphenylene sulfide is made in filtration cakes torrefaction.
The specific steps of the polyphenylene sulfide synthesis technology include:
(1) in dewatering system before polymerization, under conditions of nitrogen protection, NaHS is added in a reaction kettle, goes
Ionized water forms the aqueous solution for being 45~60%wt containing NaHS, in another reaction kettle, in the condition of nitrogen protection
Under, be added sodium hydroxide, anaerobic deionized water, formed containing sodium hydroxide be 45~60%wt aqueous solution, with will two reaction
Material in kettle is heated to 80~100 DEG C, and sodium hydrate aqueous solution input is filled the water-soluble reaction of NaHS with lye pump
In kettle, when temperature of charge reaches 120~130 DEG C, under the conditions of the temperature, after 18~30min of heat preservation generates vulcanized sodium, add
Enter N-Methyl pyrrolidone, so that Na2S:NMP molar ratio is 1.0:3.8~5.8, with the temperature rise speed of 3~6 DEG C/min, is made anti-
The temperature of material in kettle is answered to rise to 200~204 DEG C, dewatering time is 300~360min；
(2) it in the dewatering system that step (1) obtains, is added after paracide, so that the Na in polymerization system2S:p-
DCB:H2O:NMP molar ratio is 1.0:0.99~1.18:0.5~0.9:3.8~4.8, and nitrogen, juxtaposition are passed through in synthetic system
The air to swap out in polymerization system, closed polymerization reaction system carry out heat temperature raising to polymerization system immediately, when temperature rises to
When cold stage, this phase temperature is 200~210 DEG C, 2~4kg/cm of pressure2, the time is 90~135min, works as cold stage
After heat preservation terminates, temperature rises to the high temperature polymerization stage with the speed of 0.3~0.6 DEG C/min, this phase temperature is 260~270
DEG C, 8~9kg/cm of pressure2, the time is 150~180min, and after hot stage heat preservation terminates, acetic acid is added with high-pressure pump
Salt, NMP and aqueous solution make the Na of polymerization system2S:p-DCB:H2O:NMP:MAC molar ratio be 1.0:0.99~1.18:1.5~
1.9:4.8~5.8:0.8~1.1, hot stage heat preservation, temperature are 260~270 DEG C, 10~24kg/cm of pressure2, the time 30~
60min, after hot stage keeps the temperature terminate again, with the temperature of polymerization reaction system is dropped to 160~180 DEG C, while hot
Filtering, filtrate input solvent recovery system, and filter cake is to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in the filter cake that step (2) obtains, fresh nmp solvent is added, is configured to containing 13~18wt% polyphenylene sulfide
Mixture system mixture system is carried out to be heated to 160~180 DEG C, and in the temperature strip under the protection of nitrogen
It under part, after keeping the temperature 45~60min, filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
After (4) filter cake for obtaining step (3) is using purification process described in 4~6 steps (3), just obtain containing 0.1~
The polyphenylene sulfide of 0.6%wt solvent；
(5) polyphenylene sulfide for the solvent Han 0.1~0.6%wt for obtaining step (4), be added deionized water, be configured to containing
The mixture system of 13~18wt% polyphenylene sulfide is heated to mixture system under the protection of nitrogen
100 DEG C, and under the conditions of the temperature, after 45~60min of reflux heat preservation, filter while hot, filtrate is used at solvent and by-product
Reason recycling, filter cake are stand-by；
(6) after the filter cake for obtaining step (5) is using carrying out washing treatment described in 6~8 steps (5), moisture content 0.3 is just obtained
The polyphenylene sulfide of~0.6%wt；
(7) polyphenylene sulfide for the 0.3~0.6%wt of moisture content for obtaining step (6), merging temperature are 130~150 DEG C
In drier, polyphenylene sulfide has thus been made in dry 3~6h.
Wherein, the acetate in step (2) is sodium acetate, lithium acetate or calcium acetate.
Beneficial effects of the present invention:
1, the synthesis technology that the present invention uses, the metal ion on the one hand reduced in the polyphenylene sulfide being synthetically produced contain
Amount, improves the performance characteristic of polyphenylene sulfide, still further aspect improves of the polyphenylene sulfide in forming process
Grain ratio of briquetting improves polyphenylene sulfide in the purifying that purifying is closed in washing process process and closes washing effect, shortens
Purifying, washing process process and time are to make full use of NaHS and sodium hydroxide impurity phase for sulphur there are one aspect
Change the few feature of sodium, omits the treatment process process of vulcanized sodium, improve the p-DCB's in polyphenylene sulfide synthesis process
Conversion ratio, reduces the generation of polymerization reaction side reaction, and then improves the finished product yield of polyphenylene sulfide, and there are one sides
Face reduces the probability of side reaction generation, makes compound body in this way since the impurity content of the raw material in polymerization process reduces
Soluble by-products in series solvent are reduced, and are shortened the process flow of solvent recovery, are improved the recycling and reusing rate of solvent.
2, the molal quantity of sodium hydroxide is added in dehydration in the extent of corrosion of the invention in order to reduce polymerizing reactor
It is equal with NaHS, to reduce the pH value in dewatering system and polymerization reaction system, thereby reduces generation
Vulcanized sodium is under the high temperature conditions to the corrosion of polymerizing reactor.
3, the present invention is in order to improve the mouldability that polyphenylene sulfide particle is completed in synthesis, in the synthesis process, on the one hand
Make full use of the adjustability of process control condition, still further aspect, on the basis of optimizing process control condition, rationally using each
The physicochemical properties of kind auxiliary agent, after the completion of polyphenylene sulfide polycondensation, the addition acetic acid appropriate that certain mol proportion is added
Salt, NMP and water stabilize the pH value of synthetic system, and then stablize the polydispersity coefficient of the polyphenylene sulfide after synthesis and gather
The number of diphenyl sulfide resin and weight average molecular weight, further stabilizes the melt flow rate of polyphenylene sulfide, meanwhile, pass through
It is added after NMP and water, so that the capacity of the dicyandiamide solution in polymerization reaction system increases, on the one hand effectively raises by-product
The dissolving ratio of object crystal sodium chloride in water, still further aspect reduce crystal chlorine in polyphenylene sulfide particle after molding
Change the content of sodium, to reduce the sodium chloride content in polyphenylene sulfide subsequent product, and then extends polyphenylene sulfide
The application field of subsequent product.
4, the acetate, NMP and water of certain mol proportion, mesh is added after polyphenylene sulfide synthesis is completed in the present invention
Be, by further keeping the temperature, polyphenylene sulfide to be promoted to have in synthetic system under 220~230 DEG C of hot conditions
It is solidified into effect 500~1000 μm of particle, is conducive to polyphenylene sulfide synthetic system and stably cools down, on the one hand have
Effect improves the rate of temperature fall of polyphenylene sulfide synthetic system, and still further aspect effectively prevents polyphenylene sulfide and sticks
On heat exchanger coil in polymerization reaction kettle, still further aspect effectively raises polyphenylene sulfide in temperature-fall period
Grain forming, and then the impurity content in polyphenylene sulfide particle is reduced, polyphenyl is further reduced on this basis
The washing difficulty of sulfide resin.
5, in experimentation of the invention, by testing discovery repeatedly, in acetate, the NMP that certain mol proportion is added
After water, during the polymerization reaction system cooling after polymerization reaction is fully completed, rate of temperature fall is accelerated, while because
The viscosity for reducing polymerization reaction system thereby reduces bonding of the polyphenylene sulfide inside polymerizing reactor, into
When capable polymerization reaction next time, does not have to cleaning, the molar ratio of polymerization reaction system raw material will not be caused unstable.
6, in the process of the present invention, the acetate of addition can be used as the raising agent of polyphenylene sulfide, due to acetic acid
The solubility that calcium is somebody's turn to do in nmp solvent is small compared with sodium acetate, lithium acetate, meanwhile, in the synthesis process of polyphenylene sulfide, H2O
Amount in NMP is very limited, especially polyphenylene sulfide high―temperature nuclei after the reaction was completed so that acetate is containing molten
It is small when solubility in the liquid system of agent is relative to low temperature, so that acetate is present in polymerization reaction body with crystal form
In system, when polymerization reaction system temperature drops to 160 DEG C, H2O is still mainly present in polymerization reaction body in the form of water vapour
System when reducing the temperature of polymerization reaction system, can wrap up a certain amount of vinegar in such a situa-tion in polyphenylene sulfide
Hydrochlorate can thus wash the acetate for removing package in the washing process of polyphenylene sulfide, and then reduce polyphenylene sulfide
Bulk density, so that polyphenylene sulfide becomes more loose, simultaneously as after completion of the polymerization reaction, acetate is added
Molar ratio can make the acetate wrapped up in polyphenylene sulfide relatively more compared with sodium acetate with respect to sodium acetate height.
Brief description of the process of the invention:
Under the case where present invention is by first in the reaction system, being passed through the inert gases such as nitrogen or argon gas, addition centainly rubs
NaHS, sodium hydroxide, deionized water, the NMP of your ratio, are first configured to certain mass for NaHS and sodium hydroxide respectively
The aqueous solution of concentration, under the conditions of certain temperature, be mixed synthesis polyphenylene sulfide needed for raw material vulcanized sodium, by
Under the conditions of certain temperature after held for some time, thermal dehydration is being carried out to dewatering system, when temperature rises to 204 DEG C,
Dewatering time and rate of water loss are controlled, then, the paracide of certain mol proportion is filled in the case where being cooled to certain temperature
Afterwards, under conditions of closed carry out polyphenylene sulfide polymerization reaction, when temperature rises to it is certain when, under this condition
After heat preservation 4~8 hours, MAC, NMP and H of certain mol proportion are pumped into high-pressure pump immediately2O is protected under the conditions of certain temperature
Warm certain time, then cooling processing is carried out to reaction system, it when temperature drops to 160~180 DEG C, filters while hot, then with molten
Agent NMP is washed 4~7 times repeatedly, is finally washed with deionized 6~8 times, product by 120~140 DEG C be air-dried 3~
After 6h, the polyphenylene sulfide that purity is high, weight average molecular weight are high, molecular weight distribution index is narrow is obtained.
Specific embodiment
Embodiment 1
The synthesis technology of polyphenylene sulfide:
(1) under conditions of nitrogen protection, NaHS, anaerobic deionized water are added in a reaction kettle, forms sulfur-bearing hydrogen
Change the aqueous solution that sodium is 45%wt, in another reaction kettle, under conditions of nitrogen protection, sodium hydroxide is added, anaerobic is gone
Ionized water forms the aqueous solution for being 45%wt containing sodium hydroxide, with will the material in two reaction kettles be heated to 80 DEG C, use is resistance to
Alkali pump fills sodium hydrate aqueous solution input in the water-soluble reaction kettle of NaHS, when temperature of charge reaches 120 DEG C, at this
Under the conditions of temperature, after heat preservation 30min generates vulcanized sodium, N-Methyl pyrrolidone is added, so that Na2S:NMP molar ratio is
1.0:3.8 makes the temperature of material in reactor rise to 200 DEG C, dewatering time 360min with the temperature rise speed of 3 DEG C/min；
(2) it after the material in dewatering system is completed, is added after paracide, so that the Na in polymerization system2S:p-
DCB:H2O:NMP molar ratio is 1.0:0.99:0.5:3.8；It is passed through nitrogen in synthetic system, and displaces in polymerization system
Air, closed polymerization reaction system, immediately to polymerization system carry out heat temperature raising, when temperature rises to cold stage, this
Phase temperature is 200 DEG C, pressure 2kg/cm2, time 135min, after cold stage heat preservation terminates, temperature is with 0.3 DEG C/min
Speed rise to the high temperature polymerization stage, this phase temperature be 260 DEG C, pressure 8kg/cm2, time 180min, when hot stage is protected
After temperature terminates, the solution of sodium acetate, NMP and water are added with high-pressure pump, makes the Na of polymerization system2S:p-DCB:H2O:NMP:MAC
Molar ratio is 1.0:0.99:1.5:4.8:0.8, and temperature is maintained at 260 DEG C immediately, pressure 10kg/cm2, time 60min works as height
Thermophase is kept the temperature again after terminating, and with the temperature of polymerization reaction system is dropped to 160 DEG C, is filtered while hot, filtrate input is molten
Agent recovery system, filter cake are exactly to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in obtained filter cake, fresh nmp solvent is added, is configured to the mixing object containing 13wt% polyphenylene sulfide
System, under the protection of nitrogen, carries out mixture system to be heated to 160 DEG C, and under the conditions of the temperature, keeps the temperature 60min
Later, it filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
(4) technique for repeating step (3), to obtained filter cake using 4 purification process after, thus obtain containing 0.1%
The polyphenylene sulfide of wt solvent；
(5) in the polyphenylene sulfide of the obtained solvent containing 0.1%wt, deionized water is added, is configured to containing 13wt% polyphenyl
The mixture system of sulfide resin carries out mixture system to be heated to 100 DEG C, and in the temperature under the protection of nitrogen
It under the conditions of degree, after reflux heat preservation 60min, filters while hot, for filtrate for solvent and by-product processing recycling, filter cake is stand-by；
(6) repeat step (5) technique, to obtained filter cake using 6 carrying out washing treatment after, thus obtain moisture content
The polyphenylene sulfide of 0.3%wt；
(7) it by the polyphenylene sulfide of obtained moisture content 0.3%wt, is placed in the drier that temperature is 130 DEG C, dry 6h, this
Polyphenylene sulfide has just been made in sample.
Embodiment 2
The synthesis technology of polyphenylene sulfide:
(1) under conditions of nitrogen protection, NaHS, anaerobic deionized water are added in a reaction kettle, forms sulfur-bearing hydrogen
Change the aqueous solution that sodium is 60%wt, in another reaction kettle, under conditions of nitrogen protection, sodium hydroxide is added, anaerobic is gone
Ionized water forms the aqueous solution for being 60%wt containing sodium hydroxide, with will the material in two reaction kettles be heated to 100 DEG C, use is resistance to
Alkali pump fills sodium hydrate aqueous solution input in the water-soluble reaction kettle of NaHS, when temperature of charge reaches 130 DEG C, at this
Under the conditions of temperature, after heat preservation 18min generates vulcanized sodium, N-Methyl pyrrolidone is added, so that Na2S:NMP molar ratio is
1.0:5.8 makes the temperature of material in reactor rise to 204 DEG C, dewatering time 300min with the temperature rise speed of 6 DEG C/min；
(2) it after the material in dewatering system is completed, is added after paracide, so that the Na in polymerization system2S:p-
DCB:H2O:NMP molar ratio is 1.0:1.18:0.9:4.8, nitrogen is passed through in synthetic system, and displace in polymerization system
Air, closed polymerization reaction system carry out heat temperature raising, when temperature rises to cold stage, this rank to polymerization system immediately
Duan Wendu is 210 DEG C, pressure 4kg/cm2, time 90min, after cold stage heat preservation terminates, temperature is with 0.6 DEG C/min's
Speed rises to the high temperature polymerization stage, this phase temperature is 270 DEG C, pressure 9kg/cm2, time 150min, when hot stage is kept the temperature
After end, the solution of sodium acetate, NMP and water are added with high-pressure pump, makes the Na of polymerization system2S:p-DCB:H2O:NMP:MAC rubs
You are than being 1.0:1.18:1.9:5.8:1.1, and temperature is maintained at 270 DEG C immediately, pressure 24kg/cm2, time 30min works as high temperature
Stage is kept the temperature again after terminating, and with the temperature of polymerization reaction system is dropped to 180 DEG C, is filtered while hot, filtrate inputs solvent
Recovery system, filter cake are exactly to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in obtained filter cake, fresh nmp solvent is added, is configured to the mixing object containing 18wt% polyphenylene sulfide
System, under the protection of nitrogen, carries out mixture system to be heated to 180 DEG C, and under the conditions of the temperature, keeps the temperature 45min
Later, it filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
(4) technique for repeating step (3), to obtained filter cake using 6 purification process after, thus obtain containing 0.6%
The polyphenylene sulfide of wt solvent；
(5) in the polyphenylene sulfide of the obtained solvent containing 0.6%wt, deionized water is added, is configured to containing 18wt% polyphenyl
The mixture system of sulfide resin carries out mixture system to be heated to 100 DEG C, and in the temperature under the protection of nitrogen
It under the conditions of degree, after reflux heat preservation 45min, filters while hot, for filtrate for solvent and by-product processing recycling, filter cake is stand-by；
(6) repeat step (5) technique, to obtained filter cake using 8 carrying out washing treatment after, thus obtain moisture content
The polyphenylene sulfide of 0.6%wt；
(7) it by the polyphenylene sulfide of obtained moisture content 0.6%wt, is placed in the drier that temperature is 150 DEG C, dry 3h, this
Polyphenylene sulfide has just been made in sample.
Embodiment 3
The synthesis technology of polyphenylene sulfide:
(1) under conditions of nitrogen protection, NaHS, anaerobic deionized water are added in a reaction kettle, forms sulfur-bearing hydrogen
Change the aqueous solution that sodium is 48%wt, in another reaction kettle, under conditions of nitrogen protection, sodium hydroxide is added, anaerobic is gone
Ionized water forms the aqueous solution for being 52%wt containing sodium hydroxide, with will the material in two reaction kettles be heated to 83 DEG C, use is resistance to
Alkali pump fills sodium hydrate aqueous solution input in the water-soluble reaction kettle of NaHS, when temperature of charge reaches 123 DEG C, at this
Under the conditions of temperature, after heat preservation 21min generates vulcanized sodium, N-Methyl pyrrolidone is added, so that Na2S:NMP molar ratio is
1.0:4.3 makes the temperature of material in reactor rise to 203 DEG C, dewatering time 350min with the temperature rise speed of 4 DEG C/min；
(2) it after the material in dewatering system is completed, is added after paracide, so that the Na in polymerization system2S:p-
DCB:H2O:NMP molar ratio is 1.0:1.0:0.6:4.1, nitrogen is passed through in synthetic system, and displace in polymerization system
Air, closed polymerization reaction system carry out heat temperature raising, when temperature rises to cold stage, this rank to polymerization system immediately
Duan Wendu is 204 DEG C, pressure 2.7kg/cm2, time 110min, after cold stage heat preservation terminates, temperature is with 0.4 DEG C/min
Speed rise to the high temperature polymerization stage, this phase temperature be 266 DEG C, pressure 8.5kg/cm2, time 160min works as hot stage
After heat preservation terminates, the solution of lithium acetate, NMP and water are added with high-pressure pump, makes the Na of polymerization system2S:p-DCB:H2O:NMP:
MAC molar ratio is 1.0:1.0:1.7:5.3:0.9, and temperature is maintained at 263 DEG C immediately, pressure 13.8kg/cm2, the time
45min, with the temperature of polymerization reaction system is dropped to 167 DEG C, is filtered while hot after hot stage keeps the temperature terminate again,
Filtrate inputs solvent recovery system, and filter cake is exactly to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in obtained filter cake, fresh nmp solvent is added, is configured to the mixing object containing 14wt% polyphenylene sulfide
System, under the protection of nitrogen, carries out mixture system to be heated to 167 DEG C, and under the conditions of the temperature, keeps the temperature 49min
Later, it filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
(4) technique for repeating step (3), to obtained filter cake using 5 purification process after, thus obtain containing 0.2%
The polyphenylene sulfide of wt solvent；
(5) in the polyphenylene sulfide for obtaining the solvent containing 0.2%wt, deionized water is added, is configured to containing 14wt% polyphenylene sulfide
The mixture system of ether resin carries out mixture system to be heated to 100 DEG C, and in the temperature under the protection of nitrogen
Under the conditions of, it after reflux heat preservation 50min, filters while hot, for filtrate for solvent and by-product processing recycling, filter cake is stand-by；
(6) repeat step (5) technique, to obtained filter cake using 7 carrying out washing treatment after, thus obtain moisture content
The polyphenylene sulfide of 0.4%wt；
(7) it by the polyphenylene sulfide of obtained moisture content 0.4%wt, is placed in the drier that temperature is 143 DEG C, dry 3.3h,
Polyphenylene sulfide has thus been made.
Comparison example 1
(1) under conditions of nitrogen protection, NaHS, anaerobic deionized water are added in a reaction kettle, forms sulfur-bearing hydrogen
Change the aqueous solution that sodium is 45%wt, in another reaction kettle, under conditions of nitrogen protection, sodium hydroxide is added, anaerobic is gone
Ionized water forms the aqueous solution for being 45%wt containing sodium hydroxide, with will the material in two reaction kettles be heated to 80 DEG C, use is resistance to
Alkali pump fills sodium hydrate aqueous solution input in the water-soluble reaction kettle of NaHS, when temperature of charge reaches 120 DEG C, is added
N-Methyl pyrrolidone, so that Na2S:NMP molar ratio makes material in reactor for 1.0:3.8 with the temperature rise speed of 3 DEG C/min
Temperature rise to 200 DEG C, dewatering time 360min；
(2) it after the material in dewatering system is completed, is added after paracide, so that the Na in polymerization system2S:p-
DCB:H2O:NMP molar ratio is 1.0:0.99:0.5:3.8, nitrogen is passed through in synthetic system, and displace in polymerization system
Air, closed polymerization reaction system carry out heat temperature raising, when temperature rises to cold stage, this rank to polymerization system immediately
Duan Wendu is 200 DEG C, pressure 2kg/cm2, time 135min, after cold stage heat preservation terminates, temperature is with 0.3 DEG C/min's
Speed rises to the high temperature polymerization stage, and the control of this phase temperature is at 260 DEG C, pressure 8kg/cm2, time 180min works as hot stage
After heat preservation terminates, with the temperature of polymerization reaction system is dropped to 160 DEG C, to filter while hot, filtrate inputs solvent recovery system,
Filter cake is exactly to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in obtained filter cake, fresh nmp solvent is added, is configured to the mixing object containing 13wt% polyphenylene sulfide
System, under the protection of nitrogen, carries out mixture system to be heated to 160 DEG C, and under the conditions of the temperature, keeps the temperature 45min
Later, it filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
(4) technique for repeating step (3), to obtained filter cake using 4 purification process after, thus obtain containing 0.1%
The polyphenylene sulfide of wt solvent；
(5) in the polyphenylene sulfide of the obtained solvent containing 0.1%wt, deionized water is added, is configured to containing 13wt% polyphenyl
The mixture system of sulfide resin carries out mixture system to be heated to 100 DEG C, and in the temperature under the protection of nitrogen
It under the conditions of degree, after reflux heat preservation 60min, filters while hot, for filtrate for solvent and by-product processing recycling, filter cake is stand-by；
(6) repeat step (5) technique, to obtained filter cake using 6 carrying out washing treatment after, thus obtain moisture content
The polyphenylene sulfide of 0.3%wt；
(7) it by the polyphenylene sulfide of obtained moisture content 0.3%wt, is placed in the drier that temperature is 130 DEG C, dry 6h, this
Polyphenylene sulfide has just been made in sample.
The polyphenylene sulfide particle obtained by this example is in fine-powdered, with other examples polyphenyl obtained of the invention
There is apparent difference in sulfide resin particle, meanwhile, in the washing process of polyphenylene sulfide, rate of washing is at least mostly time-consuming
3h or more is detected by analysis, discovery be not added the processed polyphenylene sulfide weight average molecular weight of sodium acetate 15000 with
Under.
Embodiment 4
The synthesis technology of polyphenylene sulfide:
(1) under conditions of nitrogen protection, NaHS, anaerobic deionized water are added in a reaction kettle, forms sulfur-bearing hydrogen
Change the aqueous solution that sodium is 53%wt, in another reaction kettle, under conditions of nitrogen protection, sodium hydroxide is added, anaerobic is gone
Ionized water forms the aqueous solution for being 47%wt containing sodium hydroxide, with will the material in two reaction kettles be heated to 89 DEG C, use is resistance to
Alkali pump fills sodium hydrate aqueous solution input in the water-soluble reaction kettle of NaHS, when temperature of charge reaches 125 DEG C, at this
Under the conditions of temperature, after heat preservation 25min generates vulcanized sodium, N-Methyl pyrrolidone is added, so that Na2S:NMP molar ratio is
1.0:4.6 makes the temperature of material in reactor rise to 201 DEG C, dewatering time 330min with the temperature rise speed of 5 DEG C/min；
(2) it after the material in dewatering system is completed, is added after paracide, so that the Na in polymerization system2S:p-
DCB:H2O:NMP molar ratio is 1.0:1.03:0.8:4.5, nitrogen is passed through in synthetic system, and displace in polymerization system
Air, closed polymerization reaction system carry out heat temperature raising, when temperature rises to cold stage, this rank to polymerization system immediately
Duan Wendu is 206 DEG C, pressure 3.1kg/cm2, time 124min, after cold stage heat preservation terminates, temperature is with 0.5 DEG C/min
Speed rise to the high temperature polymerization stage, this phase temperature be 263 DEG C, pressure 8.7kg/cm2, time 168min works as hot stage
After heat preservation terminates, the solution of lithium acetate, NMP and water are added with high-pressure pump, makes the Na of polymerization system2S:p-DCB:H2O:NMP:
MAC molar ratio is 1.0:1.03:1.8:5.4:1.0, and temperature is maintained at 268 DEG C immediately, pressure 18.6kg/cm2, time 55min,
After hot stage keeps the temperature terminate again, with the temperature of polymerization reaction system is dropped to 171 DEG C, filter while hot, filtrate is defeated
Enter solvent recovery system, filter cake is exactly to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in obtained filter cake, fresh nmp solvent is added, is configured to the mixing object containing 15wt% polyphenylene sulfide
System, under the protection of nitrogen, carries out mixture system to be heated to 171 DEG C, and under the conditions of the temperature, keeps the temperature 56min
Later, it filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
(4) technique for repeating step (3), to obtained filter cake using 5 purification process after, thus obtain containing 0.5%
The polyphenylene sulfide of wt solvent；
(5) in the polyphenylene sulfide of the obtained solvent containing 0.5%wt, deionized water is added, is configured to containing 15wt% polyphenyl
The mixture system of sulfide resin carries out mixture system to be heated to 100 DEG C, and in the temperature under the protection of nitrogen
It under the conditions of degree, after reflux heat preservation 55min, filters while hot, for filtrate for solvent and by-product processing recycling, filter cake is stand-by；
(6) repeat step (5) technique, to obtained filter cake using 7 carrying out washing treatment after, thus obtain moisture content
The polyphenylene sulfide of 0.5%wt；
(7) it by the polyphenylene sulfide of obtained moisture content 0.5%wt, is placed in the drier that temperature is 141 DEG C, dry 4.5h,
Polyphenylene sulfide has thus been made.
Embodiment 5
The synthesis technology of polyphenylene sulfide:
(1) under conditions of nitrogen protection, NaHS, anaerobic deionized water are added in a reaction kettle, forms sulfur-bearing hydrogen
Change the aqueous solution that sodium is 55%wt, in another reaction kettle, under conditions of nitrogen protection, sodium hydroxide is added, anaerobic is gone
Ionized water forms the aqueous solution for being 55%wt containing sodium hydroxide, with will the material in two reaction kettles be heated to 96 DEG C, use is resistance to
Alkali pump fills sodium hydrate aqueous solution input in the water-soluble reaction kettle of NaHS, when temperature of charge reaches 126 DEG C, at this
Under the conditions of temperature, after heat preservation 28min generates vulcanized sodium, N-Methyl pyrrolidone is added, so that Na2S:NMP molar ratio is
1.0:5.3 makes the temperature of material in reactor rise to 202 DEG C with the temperature rise speed of 4.5 DEG C/min, and dewatering time is
350min；
(2) it after the material in dewatering system is completed, is added after paracide, so that the Na in polymerization system2S:p-
DCB:H2O:NMP molar ratio is 1.0:1.11:0.6:4.4, nitrogen is passed through in synthetic system, and displace in polymerization system
Air, closed polymerization reaction system carry out heat temperature raising, when temperature rises to cold stage, this rank to polymerization system immediately
Duan Wendu is 208 DEG C, pressure 3.6kg/cm2, time 129min, after cold stage heat preservation terminates, temperature is with 0.4 DEG C/min
Speed rise to the high temperature polymerization stage, this phase temperature be 268 DEG C, pressure 8.6kg/cm2, time 173min works as hot stage
After heat preservation terminates, the solution of calcium acetate, NMP and water are added with high-pressure pump, makes the Na of polymerization system2S:p-DCB:H2O:NMP:
MAC molar ratio is 1.0:1.11:1.8:5.6:1.05, and temperature is maintained at 266 DEG C immediately, pressure 19.3kg/cm2, the time
50min, with the temperature of polymerization reaction system is dropped to 166 DEG C, is filtered while hot after hot stage keeps the temperature terminate again,
Filtrate inputs solvent recovery system, and filter cake is exactly to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in obtained filter cake, fresh nmp solvent is added, is configured to the mixing object containing 17wt% polyphenylene sulfide
System, under the protection of nitrogen, carries out mixture system to be heated to 165 DEG C, and under the conditions of the temperature, keeps the temperature 54min
Later, it filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
(4) repeat step (3) technique, to obtained filter cake using 4 purification process after, thus contained
The polyphenylene sulfide of 0.43%wt solvent；
(5) in the polyphenylene sulfide of the obtained solvent containing 0.43%wt, deionized water is added, is configured to containing 17wt% polyphenyl
The mixture system of sulfide resin carries out mixture system to be heated to 100 DEG C, and in the temperature under the protection of nitrogen
It under the conditions of degree, after reflux heat preservation 57min, filters while hot, for filtrate for solvent and by-product processing recycling, filter cake is stand-by；
(6) repeat step (5) technique, to obtained filter cake using 7 carrying out washing treatment after, thus obtain moisture content
The polyphenylene sulfide of 0.5%wt；
(7) it by the polyphenylene sulfide of obtained moisture content 0.5%wt, is placed in the drier that temperature is 137 DEG C, dry 5.6h,
Polyphenylene sulfide has thus been made.
Embodiment 6
The synthesis technology of polyphenylene sulfide:
(1) under conditions of nitrogen protection, NaHS, anaerobic deionized water are added in a reaction kettle, forms sulfur-bearing hydrogen
Change the aqueous solution that sodium is 49%wt, in another reaction kettle, under conditions of nitrogen protection, sodium hydroxide is added, anaerobic is gone
Ionized water forms the aqueous solution for being 60%wt containing sodium hydroxide, with will the material in two reaction kettles be heated to 91 DEG C, use is resistance to
Alkali pump fills sodium hydrate aqueous solution input in the water-soluble reaction kettle of NaHS, when temperature of charge reaches 124 DEG C, at this
Under the conditions of temperature, after heat preservation 24min generates vulcanized sodium, N-Methyl pyrrolidone is added, so that Na2S:NMP molar ratio is
1.0:5.6 makes the temperature of material in reactor rise to 204 DEG C, dewatering time 360min with the temperature rise speed of 6 DEG C/min；
(2) it in obtained dewatering system, is added after paracide, so that the Na in polymerization system2S:p-DCB:H2O:
NMP molar ratio is 1.0:1.16:1.3:4.4, nitrogen is passed through in synthetic system, and displace the air in polymerization system, close
Polymerization reaction system is closed, heat temperature raising is carried out to polymerization system immediately, when temperature rises to cold stage, this phase temperature is
210 DEG C, pressure 4kg/cm2, time 135min, after cold stage heat preservation terminates, temperature is risen to the speed of 0.6 DEG C/min
High temperature polymerization stage, this phase temperature are 270 DEG C, pressure 9kg/cm2, time 180min, after hot stage heat preservation terminates,
The solution of calcium acetate, NMP and water are added with high-pressure pump, makes the Na of polymerization system2S:p-DCB:H2O:NMP:MAC molar ratio is
1.0:1.16:2.3:5.8:1.1, temperature is maintained at 268 DEG C immediately, pressure 21.8kg/cm2, time 60min works as high temperature
Stage is kept the temperature again after terminating, and with the temperature of polymerization reaction system is dropped to 160 DEG C, is filtered while hot, filtrate inputs solvent
Recovery system, filter cake are exactly to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in obtained filter cake, fresh nmp solvent is added, is configured to the mixing object containing 18wt% polyphenylene sulfide
System, under the protection of nitrogen, carries out mixture system to be heated to 180 DEG C, and under the conditions of the temperature, keeps the temperature 60min
Later, it filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
(4) technique for repeating step (3), to obtained filter cake using 6 purification process after, thus obtain containing 0.3%
The polyphenylene sulfide of wt solvent；
(5) by the polyphenylene sulfide of the obtained solvent containing 0.3%wt, deionized water is added, is configured to containing 18wt% polyphenylene sulfide
The mixture system of ether resin carries out mixture system to be heated to 100 DEG C, and in the temperature under the protection of nitrogen
Under the conditions of, it after reflux heat preservation 60min, filters while hot, for filtrate for solvent and by-product processing recycling, filter cake is stand-by；
(6) repeat step (5) technique, to obtained filter cake using 8 carrying out washing treatment after, thus obtain moisture content
The polyphenylene sulfide of 0.6%wt；
(7) it by the polyphenylene sulfide of obtained moisture content 0.6%wt, is placed in the drier that temperature is 150 DEG C, dry 6h, this
Polyphenylene sulfide has just been made in sample.
Comparison example 2
(1) under conditions of nitrogen protection, the NaHS and sodium hydroxide, anaerobic that molar ratio is 1:1 are added in a kettle
Deionized water, to form Containing Sulfur sodium as the aqueous solution of 60%wt, when temperature of charge reaches 130 DEG C, under the conditions of the temperature,
After keeping the temperature 130min generation vulcanized sodium, N-Methyl pyrrolidone is added, so that Na2S:NMP molar ratio is 1.0:5.8, with 6
DEG C/temperature rise speed of min, so that the temperature of material in reactor is risen to 204 DEG C, dewatering time 300min.
(2) it after the material in dewatering system is completed, is added after paracide, so that in polymerization system
Na2S:p-DCB:H2O:NMP molar ratio is 1.0:1.18:0.9:4.8, nitrogen is passed through in synthetic system, and displace condensate
Air in system, closed polymerization reaction system carry out heat temperature raising to polymerization system immediately, when temperature rises to cold stage
When, this phase temperature is 210 DEG C, pressure 2kg/cm2, time 135min, after cold stage heat preservation terminates, temperature is with 0.6
DEG C/speed of min rises to the high temperature polymerization stage, this phase temperature is 270 DEG C, pressure 9kg/cm2, time 180min works as high temperature
After stage heat preservation terminates, with the temperature of polymerization reaction system is dropped to 180 DEG C, filter while hot, filtrate inputs solvent recovery
System, filter cake are exactly to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in obtained filter cake, fresh nmp solvent is added, is configured to the mixing object containing 18wt% polyphenylene sulfide
System, under the protection of nitrogen, carries out mixture system to be heated to 180 DEG C, and under the conditions of the temperature, keeps the temperature 60min
Later, it filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
(4) technique for repeating step (3), to obtained filter cake using 6 purification process after, thus obtain containing 0.3%
The polyphenylene sulfide of wt solvent；
(5) in the polyphenylene sulfide of the obtained solvent containing 0.3%wt, deionized water is added, is configured to containing 18wt% polyphenyl
The mixture system of sulfide resin carries out mixture system to be heated to 100 DEG C, and in the temperature under the protection of nitrogen
It under the conditions of degree, after reflux heat preservation 60min, filters while hot, for filtrate for solvent and by-product processing recycling, filter cake is stand-by；
(6) repeat step (5) technique, to obtained filter cake using 8 carrying out washing treatment after, thus obtain moisture content
The polyphenylene sulfide of 0.6%wt；
(7) polyphenylene sulfide of moisture content 0.6%wt will be obtained, is placed in the drier that temperature is 150 DEG C, dry 3h, in this way
Polyphenylene sulfide has just been made.
The polyphenylene sulfide particle that the application obtains is in fine-powdered, compared to comparison example polyphenylene sulfide resin obtained
There is apparent difference in rouge particle, meanwhile, in the washing process of polyphenylene sulfide, at least more time-consuming 4h of rate of washing with
On, it detects by analysis, the processed polyphenylene sulfide weight average molecular weight of sodium acetate is not added below 13000 for discovery.
Claims (2)
1. a kind of polyphenylene sulfide synthesis technology, which is characterized in that the technique includes:
(1) in dewatering system before polymerization, under conditions of nitrogen protection, NaHS is added in a reaction kettle, goes
Ionized water forms the aqueous solution for being 45~60%wt containing NaHS, in another reaction kettle, in the condition of nitrogen protection
Under, be added sodium hydroxide, anaerobic deionized water, formed containing sodium hydroxide be 45~60%wt aqueous solution, with will two reaction
Material in kettle is heated to 80~100 DEG C, and sodium hydrate aqueous solution input is filled the water-soluble reaction of NaHS with lye pump
In kettle, when temperature of charge reaches 120~130 DEG C, under the conditions of the temperature, after 18~30min of heat preservation generates vulcanized sodium, add
Enter N-Methyl pyrrolidone, so that Na2S:NMP molar ratio is 1.0:3.8~5.8, with the temperature rise speed of 3~6 DEG C/min, is made anti-
The temperature of material in kettle is answered to rise to 200~204 DEG C, dewatering time is 300~360min；
(2) it in the dewatering system that step (1) obtains, is added after paracide, so that the Na in polymerization system2S:p-
DCB:H2O:NMP molar ratio is 1.0:0.99~1.18:0.5~0.9:3.8~4.8, and nitrogen, juxtaposition are passed through in synthetic system
The air to swap out in polymerization system, closed polymerization reaction system carry out heat temperature raising to polymerization system immediately, when temperature rises to
When cold stage, this phase temperature is 200~210 DEG C, 2~4kg/cm of pressure2, the time is 90~135min, works as cold stage
After heat preservation terminates, temperature rises to the high temperature polymerization stage with the speed of 0.3~0.6 DEG C/min, this phase temperature is 260~270
DEG C, 8~9kg/cm of pressure2, the time is 150~180min, and after hot stage heat preservation terminates, acetic acid is added with high-pressure pump
Salt, NMP and aqueous solution make the Na of polymerization system2S:p-DCB:H2O:NMP:MAC molar ratio be 1.0:0.99~1.18:1.5~
1.9:4.8~5.8:0.8~1.1, hot stage heat preservation, temperature are 260~270 DEG C, 10~24kg/cm of pressure2, the time 30~
60min, after hot stage keeps the temperature terminate again, with the temperature of polymerization reaction system is dropped to 160~180 DEG C, while hot
Filtering, filtrate input solvent recovery system, and filter cake is to be synthetically produced out the polyphenylene sulfide containing certain impurity；
(3) in the filter cake that step (2) obtains, fresh nmp solvent is added, is configured to containing 13~18wt% polyphenylene sulfide
Mixture system mixture system is carried out to be heated to 160~180 DEG C, and in the temperature strip under the protection of nitrogen
It under part, after keeping the temperature 45~60min, filters while hot, processing recycling of the filtrate for solvent and by-product, filter cake is stand-by；
After (4) filter cake for obtaining step (3) is using purification process described in 4~6 steps (3), just obtain containing 0.1~
The polyphenylene sulfide of 0.6%wt solvent；
(5) polyphenylene sulfide for the solvent Han 0.1~0.6%wt for obtaining step (4), be added deionized water, be configured to containing
The mixture system of 13~18wt% polyphenylene sulfide is heated to mixture system under the protection of nitrogen
100 DEG C, and under the conditions of the temperature, after 45~60min of reflux heat preservation, filter while hot, filtrate is used at solvent and by-product
Reason recycling, filter cake are stand-by；
(6) after the filter cake for obtaining step (5) is using carrying out washing treatment described in 6~8 steps (5), moisture content 0.3 is just obtained
The polyphenylene sulfide of~0.6%wt；
(7) polyphenylene sulfide for the 0.3~0.6%wt of moisture content for obtaining step (6), merging temperature are 130~150 DEG C
In drier, polyphenylene sulfide has thus been made in dry 3~6h.
2. a kind of polyphenylene sulfide synthesis technology according to claim 1, it is characterised in that: vinegar described in step (2)
Hydrochlorate is sodium acetate, lithium acetate or calcium acetate.
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| CN110628219A (en) * | 2019-09-27 | 2019-12-31 | 陈逊 | Manufacturing process of polyphenylene sulfide film |
| CN111171320A (en) * | 2020-02-13 | 2020-05-19 | 四川明道和化学新材料有限公司 | Production method of catalyst-removed polyphenylene sulfide resin |
| CN111471177A (en) * | 2020-05-11 | 2020-07-31 | 山东滨化滨阳燃化有限公司 | Industrial production process and device of fiber-grade polyphenylene sulfide resin |
| CN112940255A (en) * | 2021-04-14 | 2021-06-11 | 深圳市华盈新材料有限公司 | Purification treatment process of polyphenylene sulfide resin |
| CN113004520A (en) * | 2021-04-14 | 2021-06-22 | 深圳市华盈新材料有限公司 | Synthetic process of polyphenylene sulfide resin |
| CN115073737A (en) * | 2022-04-28 | 2022-09-20 | 新疆中泰新鑫化工科技股份有限公司 | Temperature control method and device for polyphenylene sulfide polymerization reaction |
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| CN110628219A (en) * | 2019-09-27 | 2019-12-31 | 陈逊 | Manufacturing process of polyphenylene sulfide film |
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| CN111171320A (en) * | 2020-02-13 | 2020-05-19 | 四川明道和化学新材料有限公司 | Production method of catalyst-removed polyphenylene sulfide resin |
| CN111171320B (en) * | 2020-02-13 | 2022-05-06 | 四川明道和化学新材料有限公司 | Production method of catalyst-removed polyphenylene sulfide resin |
| CN111471177A (en) * | 2020-05-11 | 2020-07-31 | 山东滨化滨阳燃化有限公司 | Industrial production process and device of fiber-grade polyphenylene sulfide resin |
| CN112940255A (en) * | 2021-04-14 | 2021-06-11 | 深圳市华盈新材料有限公司 | Purification treatment process of polyphenylene sulfide resin |
| CN113004520A (en) * | 2021-04-14 | 2021-06-22 | 深圳市华盈新材料有限公司 | Synthetic process of polyphenylene sulfide resin |
| CN112940255B (en) * | 2021-04-14 | 2023-02-17 | 深圳市华盈新材料有限公司 | Purification treatment process of polyphenylene sulfide resin |
| CN115073737A (en) * | 2022-04-28 | 2022-09-20 | 新疆中泰新鑫化工科技股份有限公司 | Temperature control method and device for polyphenylene sulfide polymerization reaction |
| CN115073737B (en) * | 2022-04-28 | 2023-11-24 | 新疆中泰新鑫化工科技股份有限公司 | Temperature control method and device for polyphenylene sulfide polymerization reaction |
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