CN106750299B - A kind of preparation method of low cost polyphenylene sulfide - Google Patents
A kind of preparation method of low cost polyphenylene sulfide Download PDFInfo
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- CN106750299B CN106750299B CN201710026395.6A CN201710026395A CN106750299B CN 106750299 B CN106750299 B CN 106750299B CN 201710026395 A CN201710026395 A CN 201710026395A CN 106750299 B CN106750299 B CN 106750299B
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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
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- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
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- 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
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- C08G75/0204—Polyarylenethioethers
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Abstract
The invention discloses a kind of preparation methods of inexpensive polyphenylene sulfide, it is related to polymeric material field, with vulcanized sodium, paracide is raw material, with sodium benzoate, caprolactone is catalyst, using N-Methyl pyrrolidone as solvent, using sodium hydroxide as auxiliary agent, its concrete technology flow process produced successively feeds intake including vulcanized sodium, paracide feeds intake, the dissolution of catalyst, prepolymerization, it polymerize again, filtering, washing, it is dry, packing department, finally obtain polyphenylene sulfide product, the present invention has abandoned the chlorination lithium catalyst that existing domestic prevailing technology uses, using the sodium benzoate of low cost and caprolactone as catalyst, reduce production cost, the method that all raw materials are added dropwise by several times using normal pressure, carry out polymerization reaction in certain temperature range, effectively prevent heat release implode when polymerization reaction, improve the degree of polymerization of polyphenylene sulfide With various mechanical performances, thoroughly solve the problems, such as that traditional handicraft product is unstable, molecular weight is not high, performance is poor.
Description
Technical field
The present invention relates to polymeric material field, more particularly to a kind of preparation side of inexpensive polyphenylene sulfide
Method.
Background technique
Polyphenylene sulfide has excellent thermal stability, chemical stability, corrosion resistance and electrical property, and inorganic fills out with various
Material has good compatibility, can be compound with various inorganic fillers and other high molecular materials, and the various engineerings haveing excellent performance are made
Plastics and blend alloy.In addition, the dimensional stability of polyphenylene sulfide (PPS) product is prominent, almost all of plastics can be used and add
Work method is processed, including spraying, injection molding, compression moulding, extrusion, blowing and encapsulating etc., also can carry out secondary operation to product.Cause
This, polyphenylene sulfide (PPS) automobile manufacture, electronics, machinery, machinery manufacture, chemical industry instrument and meter and in terms of have
It is widely applied, is known as the sixth-largest engineering plastics, exploitation prospect is very wide.
The synthetic method of current polyphenylene sulfide has:
1, sodium sulfide method.PPS is made by condensation reaction in polar solvent with paracide and anhydrous sodium sulfide.The method
It is using anhydrous sodium sulfide and Isosorbide-5-Nitrae-dichloro-benzenes as raw material, alkali metal salt reacts polycondensation in highly polar proton solvent as auxiliary agent
Prepare PPS.
2, sulfur solution route.It is the distinctive synthesis polyphenylene sulfide process route in China, the practical sulphur of this method replaces vulcanized sodium
As sulphur source, within the scope of 175-250 DEG C, as raw material, metal and low valence metal ion salt and have using paracide and sulphur
Machine acids etc. makees catalyst, and polycondensation reaction occurs under normal pressure in polar solvent and prepares PPS, it is crucial that sulfur solution route prepares PPS
It is the fracture of eight ring of sulphur, the generation of sulphur anion.
3, hydrogen sulfide method.A certain amount of tertiary sodium phosphate is added using hydrogen sulfide, sodium hydroxide and paracide as raw material in the method
Make auxiliary agent, normal pressure polycondensation reaction is carried out in polar solvent hexamethylphosphorictriamide (HMPA).
4, oxidation polymerization route.The method is with Diphenyl disulfide ether (DSP) for raw material, and oxygen or air are oxidant, second
Sour acetone oxidation vanadium or Lewis acid are catalyst, react PPS is made at normal temperatures and pressures.
5, to halogenated benzenethiol salt from polycondensation route.To halogenated benzenethiol, halogenated methyl benzenethiol, halogenated multiple phenyl sulphur
The alkali metal salt of phenol and these salt replaced by alkyl, aromatic core substituent group after derivative, in N2It can be carried out in the presence of pyridine
Itself polycondensation.
The above technology there are the problem of be respectively as follows:
1, it uses lithium chloride for catalyst, increases production cost.
2, the PPS molecular weight synthesized is not high, lot stability is bad.
3, synthesis condition is harsh, and the device is complicated, higher cost, and manufacture energy consumption is high.
The Phillips Petroleum Company in the U.S. develops the Industrialized synthesis method of PPS in six the seventies of twentieth century,
The said firm proposes that n-methyl-2-pyrrolidone is solvent using vulcanized sodium and paracide as raw material for the first time, through dehydration and
Polycondensation process obtains the PPS resin that fusing point is greater than 275 DEG C, and realizes the industrialized production of PPS for the first time in 1971, in morning
Phase, the molecular weight product produced with this method is lower (weight average molecular weight is lower than 2 × 104), thus shock resistance is poor；And by
In the presence of inorganic salts, moisture-proof, the mouldability of product are also poor.For reduce resin mobility to meet process requirements,
The early stage production of PPS usually improves molecular weight by oxidation cross-linked mode.
In the United States Patent (USP) of Patent No. US4728231, for the technological improvement of the lower problem proposition of molecular weight product
Method are as follows: by the addition alkali metal carboxylate in melting polyphenylene sulfide and water reaction chain extension, then polyphenylene sulfide is precipitated to increase
Add molecular weight, but this reaction carries out under high-temperature and high-pressure conditions, condition is harsh, and the device is complicated, higher cost.
Japanese Kureha Kagaku Kogyo K.K. has also applied for a large amount of Japan to the PPS resin synthesis technology of different performance
Patent (such as: tekiaki 62-253626, tekiaki 2004-24619).The method that retraction reaction process generallys use second-stage reaction
To obtain satisfactory PPS resin, the said firm also refers to similar PPS in the patent CN88108247.3 of China's application
Synthetic technology of resins, but the manufacture energy consumption of PPS is not illustrated accordingly, in actual production, produce in the method also really
There is a problem of that manufacture energy consumption is high.
China starts the synthesis to PPS resin the 1970s and studies with application, and correlative study and production are looked forward to
Industry has also applied for some Chinese patents (such as CN85102554A, CN00116141.5, CN1793202A, CN104877167).
Currently, domestic main PPS manufacturer is that Honghe Chemical Industry Co. Ltd. Zigong, Zhejiang newly synthesize the limited public affairs of special material
Department etc..Chinese PPS synthesis mostly uses lithium chloride for catalyst, but with the rising of lithium chloride cost in recent years, causes to produce
Increased costs are badly in need of finding cheap catalyst substitution.And the PPS molecular weight of synthesis is not high, lot stability is difficult to control.
Summary of the invention
The present invention provides a kind of preparation method of inexpensive polyphenylene sulfide, avoids reducing production cost using lithium chloride, with
The PPS molecular weight of solution prior art synthesis is not high, lot stability is bad, synthesis condition is harsh, the device is complicated, higher cost
And the problem that manufacture energy consumption is high.
In order to solve the above technical problems, the invention adopts the following technical scheme:
A kind of preparation method of low cost polyphenylene sulfide, using vulcanized sodium, paracide as raw material, with N-Methyl pyrrolidone
For solvent, using sodium benzoate, caprolactone as catalyst, using sodium hydroxide as auxiliary agent, the concrete technology flow process of production includes such as
Lower step:
(1) vulcanized sodium feeds intake: vulcanized sodium, sodium hydroxide are successively put into dehydrating kettle, N-Methyl pyrrolidone is added,
Nitrogen protection is then passed to, stirring is opened, which is risen to 130-200 DEG C and is maintained；
(2) dissolution of paracide: paracide is put into paracide dissolution kettle, and N-Methyl pyrrolidone is added,
Stirring is started, under the protection of nitrogen, which is risen to 70-150 DEG C, until paracide is dissolved in N- methylpyrrole
In alkanone；
(3) dissolution of catalyst: N-Methyl pyrrolidone is first added in catalyst dissolution kettle, then puts into catalyst, so
After be passed through nitrogen protection, start stirring, which, which is risen to 70-150 DEG C, makes catalyst be dissolved in N-Methyl pyrrolidone
In；
(4) prepolymerization: the 1/3-1/2 for the liquor capacity that step (2) are prepared and step (3) solution prepared are delivered to
In the dehydrating kettle of step (1), it is passed through nitrogen protection, opens stirring, which is maintained at 130-200 DEG C, reaction 2-4 is small
When, during which to the discharge liquor and gas progress analysis detection in reaction；
(5) it polymerize again: is passed through nitrogen protection, opens stirring, the prepolymerization liquid that step (4) obtains is delivered to polymerization
In kettle, the system temperature is first down to 120-170 DEG C, the remaining part for the solution that step (2) are prepared then is delivered to polymerization
In kettle, then the system temperature is maintained at 180-280 DEG C, 5-10 hour reacted, after reaction, by the mixing in polymeric kettle
Object is put into spraying seperator, using being centrifugated into polyphenylene sulfide particle；
(6) it is filtered, washed, dries, being packaged to be polyphenylene sulfide product.
Preferably, the molfraction for participating in each component of reaction is respectively as follows:
Vulcanized sodium 1.0-1.5, paracide 1.0-1.6, sodium benzoate 0.05-0.15, caprolactone 0.05-0.15, hydrogen-oxygen
The molfraction of change sodium 0.05-0.5, solvent N-methyl pyrilidone additional amount and paracide input amount is 5-10.
Preferably, the tail gas that displacement nitrogen generates in step (1)-step (5) enters exhaust gas processing device and removes harmful gas
It is vented after body.Preferably, gaseous substance formed in the dehydrating kettle of step (1) enters condensation through the top duct of dehydrating kettle
Device, condensed liquid enter condensate tank, are sent to solvent recovery process recycling N-Methyl pyrrolidone, condensed
Remaining tail gas, which enters after decompression after exhaust gas processing device removes pernicious gas, to be vented.
Preferably, the recovery process includes the following steps:
(1) it wash water and the recycling of by-product salt: is carried out in dehydrating tower, the gas after evaporation, which enters in overhead condenser, to be condensed into
Water, partial reflux to dehydrating tower, partial condensation water are delivered in storage tank；Tower bottom liquid after evaporation is to contain by-product salt and impure
N-Methyl pyrrolidone, send to equipment for separating liquid from solid and be separated by solid-liquid separation, isolated solid is by-product salt, and by-product salt send
It is dry to drying machine；
(2) N-Methyl pyrrolidone recycles: in the isolated liquid of step (1), being delivered to N-Methyl pyrrolidone and returns
Tower is received, by tower bottom reboiler heat temperature raising, the gas after evaporation, which enters in overhead condenser, is condensed into liquid N- methylpyrrole
Alkanone, partial reflux are delivered in storage tank to de- N-Methyl pyrrolidone tower, part N-Methyl pyrrolidone.
Preferably, gaseous substance formed in the dehydrating kettle of step (4) and the polymeric kettle of step (5) through dehydrating kettle or
The top duct of polymeric kettle enters condenser, and condensed liquid enters condensate tank, is sent to solvent and catalyst returns
Sequence of knocking off recycling design and catalyst, condensed remnants tail gas enter exhaust gas processing device after decompression and remove pernicious gas
After be vented.
Preferably, step (6) concrete operations are as follows:
(1) it filters: by solidliquid mixture obtained in spraying seperator with the filtering of 1# horizontal spiral filter is pumped to, filtering
Liquid is sent into solvent and catalyst recovery process recycling design and catalyst, and filter cake remains to handle in next step；
(2) wash: the filter cake being obtained by filtration enters six rinsing bowls by 1# screw conveyor, pre- in six wash water kettles
The wash water that last time washing is added in five wash water pumps is first passed through, starts agitator treating 20-40 minutes, slurries are pumped with six rinsing bowls
Entering the filtering of 2# horizontal spiral filter, filter cake enters five rinsing bowls by 2# screw conveyor, and filtrate enters six wash water slots,
Wash water is pumped into recovery process by six wash waters；Secondary wash water is added by secondary wash water pump in advance in five rinsing bowls, starts and stirs
It mixes, filter cake washs 20-40 minutes after entering, and slurries are pumped into 3# horizontal spiral filter with five rinsing bowls and filter, and filter cake is logical
3# screw conveyor is crossed into four rinsing bowls, filtrate enters the washing lotion that five wash water slots are used as six rinsing bowls；Four washings
It is previously added wash water in slot, starts stirring, the material washing by soaking sent by 3# screw conveyor 3-4 hours, slurries are with four times
Rinsing bowl is pumped into the filtering of 4# horizontal spiral filter, and filter cake enters rinsing bowl three times by 4# screw conveyor, and filtrate enters
Four wash water slots, wash water are pumped into sewage treatment process by four wash waters；A water is previously added in rinsing bowl three times, filter cake adds
After entering, stirring is started, is washed about 30 minutes, slurries are pumped into 5# horizontal spiral filter with rinsing bowl three times and filter, and filter cake is logical
5# screw conveyor is crossed into secondary rinsing bowl, filtrate is into wash water slot, wash water are pumped into solvent recovery by wash water three times three times
Destructive distillation slot；Be previously added in secondary rinsing bowl by once wash pumping come primary wash liquor, filter cake addition after, start stirring, wash
Wash 20-40 minutes, slurries with secondary rinsing bowl be pumped into 6# horizontal spiral filter filter, filter cake by 6# screw conveyor into
Enter a rinsing bowl, filtrate enters secondary wash water slot, and wash water is pumped into five rinsing bowls by secondary wash water as cleaning solution；One
It is previously added deionized water in secondary rinsing bowl, after filter cake is added, starts stirring, washs 20-40 minutes, rinsing bowl of slurries
It is pumped into the filtering of 7# horizontal spiral filter, filter cake enters fluidized bed by 8# screw conveyor and is dried, and filtrate enters one
Secondary wash water slot is continued to employ；
(3) dry, packaging: the filter cake being obtained by filtration after primary washing, which enters fluidized bed by 8# screw conveyor, to be done
Dry, the resin after drying is directly entered the sending warehouse of flow delivery systems, packaging feed bin is transported to by air-flow, by packing automatically
And packaging becomes finished product, tail gas empties after deduster purifies.
Preferably, the recovery process is used to recycle the sodium chloride that mass content is 8-15% in washing water, passes sequentially through
Dehydration, separation, the washing of raw salt, centrifugal dehydration, dry packing operation.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention has abandoned existing domestic prevailing technology and has used on the basis of conventional vulcanized sodium method produces PPS resin
Chlorination lithium catalyst prepare that capability and performance is stable and cost using the sodium benzoate of low cost and caprolactone as catalyst
Lower polyphenylene sulfide, chlorination lithium catalyst present price ten thousand/ton of 12-15 sale that prevailing technology uses domestic at present
Valence accounts for cost of material 30-37.5%, and the PPS using the produced in conventional processes of lithium chloride is at high cost, uncontested advantage, state expert
Industry is in the edge that loses and get a profit, and uses the sodium benzoate and caprolactone mixed catalyst of factory formula of the present invention and low cost
Process flow can then save ten thousand yuan/ton of 2-3 of cost, and the superior product quality of output, price are low；
(2) method that all raw materials of the present invention are added dropwise by several times using normal pressure, make polymerization reaction in certain temperature range into
Row, effectively prevents heat release implode when polymerization reaction, improves the degree of polymerization and various mechanical performances of polyphenylene sulfide, this method
Stability is good, reproducibility is high, thoroughly solves the problems, such as that traditional handicraft product is unstable, molecular weight is not high, performance is poor；
(3) low energy consumption of the present invention is mixed using the sodium benzoate and caprolactone of factory formula of the present invention and low cost
After the process route of catalyst, the synthesizing section period reduces, and auxiliary agent recovery process is more simple, and energy consumption reduces, three waste discharge
Greatly reduce.
Specific embodiment
Application principle, effect and effect of the invention, is explained by the way that mode is implemented as follows.
Embodiment 1
Before launching production, purity first is carried out to paracide, vulcanized sodium, N-Methyl pyrrolidone, sodium hydroxide, catalyst
Analysis, to avoid later period production is influenced.
By taking the injected volume of 100Kg paracide as an example, proceed as follows:
(1) vulcanized sodium feeds intake:
The exhaust valve for leading to exhaust gas processing device that dehydrating kettle is first opened before charging, releases the pressure in dehydrating kettle
It puts.
The whole package piece shape technical pure vulcanized sodium of 52Kg is transported to dehydration workshop, elevator by trolley in storehouse
Floor where mentioning between unpacking is transported between the unpacking of closed ventilation, vulcanized sodium is unpacked and is put into feed hopper, is added simultaneously
Vulcanized sodium and sodium hydroxide are discharged into dehydrating kettle by 2.5kg sodium hydroxide by feed hopper；
N- first is sent into from N-Methyl pyrrolidone pump from solvent storage tank to the N-Methyl pyrrolidone measuring tank with reflux
The N-Methyl pyrrolidone of 300kg is added from N-Methyl pyrrolidone measuring tank into dehydrating kettle for base pyrrolidones；Simultaneously with N-
Methyl pyrrolidone (in self-measuring slot) is flushed into hopper, makes vulcanized sodium and sodium hydroxide completely into dehydrating kettle, is passed through nitrogen
Gas excludes air in kettle, starts stirring, under the protection of nitrogen, is gradually warming up to 130- to mixture by the steam in collet
200℃。
It is formed by gaseous substance during this step operation and enters condenser, condensed liquid enters condensate liquid storage
Tank is sent to recovery process recycling N-Methyl pyrrolidone after reaching certain liquid level, and remaining tail gas enters washing tail gas by decompression
Tower is vented after removing the pernicious gases such as hydrogen sulfide.
(2) dissolution of paracide:
The exhaust valve that dissolution kettle leads to tail gas absorber is first opened before charging, discharges the pressure in dissolution kettle.
The whole packet paracide of 100Kg in storehouse is transported to dehydration workshop by trolley, elevator is mentioned to unpacking
Between where floor, be transported between the unpacking of closed ventilation, paracide unpacked and is put into feed hopper, will be to two by feed hopper
Chlorobenzene is discharged into dissolution kettle；
It is sent into from N-Methyl pyrrolidone pump from solvent storage tank to the dissolution N-Methyl pyrrolidone measuring tank with reflux
The N-Methyl pyrrolidone of 50kg is added from dissolution N-Methyl pyrrolidone measuring tank into dissolution kettle for N-Methyl pyrrolidone；
Hopper is flushed into N-Methyl pyrrolidone (in self-measuring slot) simultaneously, makes paracide completely into dissolution kettle, is passed through nitrogen
Gas excludes air in kettle, and remaining tail gas, which enters after tail gas washing tower removes pernicious gas, to be vented, and stirring is started, in the protection of nitrogen
Under, it is gradually warming up to 150 DEG C to mixture by the steam in collet, is dissolved in paracide in N-Methyl pyrrolidone.
(3) dissolution of catalyst
The N-Methyl pyrrolidone that 100kg is added into catalyst dissolution kettle is pumped with N-Methyl pyrrolidone, is catalyzed in dress
The exhaust valve that catalyst dissolution kettle leads to tail gas absorber is first opened before agent, discharges the pressure in catalyst dissolution kettle；It is logical
8Kg sodium benzoate and 8Kg caprolactone are added into catalyst dissolution kettle for too small hopper, and with the N- crassitude of 10kg or so
Ketone rinses hopper, closes charging.
The N-Methyl pyrrolidone of 100kg is added into catalyst dissolution kettle again, closes valve, is passed through nitrogen, replaces nitrogen
Tail gas after gas behind absorption tower by being vented；Nitrogen valve is closed, is heated by jacket steam, dissolves catalyst.
(4) prepolymerization
The complete soln pump that solution and step (3) that 60kg step (2) are prepared are prepared is delivered in step (1)
Dehydrating kettle, under the protection of nitrogen, stirring is started, and is maintained at 180~200 DEG C by jacket steam heating temperature, reaction 2 is small
When, carry out prepolymerization.
Period in reaction discharge liquor and gas carry out analysis detection, with the prepolymerized process of determination.
During this step operation
It is formed by gaseous substance and enters condenser, condensed liquid enters condensate tank, is sent to recycling work
Sequence recycling design and catalyst, remaining tail gas are put by depressurizing to enter after exhaust gas processing device removes the pernicious gases such as hydrogen sulfide
It is empty.
(5) it polymerize again
Polymeric kettle stirring is started, with nitrogen by air displacement in polymeric kettle, tail gas is emptied by tail gas washing tower；Step
(5) the pre-polymer solution pump obtained is delivered in polymeric kettle, and cooling water is led in jacket of polymerization makes prepolymer temperature in kettle
100~120 DEG C are down to, is sent remaining 90kg paracide-N-Methyl pyrrolidone solution to polymeric kettle with pump, collet
Continue logical cooling water or steam, makes to polymerize temperature in the kettle control at 180~200 DEG C, react 6 hours.
After reaction, mixture in reaction kettle is put into spraying seperator, using being centrifugated into polyphenylene sulfide
Grain.
It is formed by gaseous substance during this step operation and enters condenser, condensed liquid enters condensate liquid storage
Tank, is sent to recovery process recycling design and catalyst, and remaining tail gas enters tail gas washing tower by decompression and removes hydrogen sulfide
It is vented after equal pernicious gases.
(6) it is filtered, washed, dries, packaging process:
1. filtering: by solidliquid mixture obtained in spraying seperator with the filtering of 1# horizontal spiral filter is pumped to, filtering
Liquid is sent into solvent and catalyst recovery process recycling design and catalyst, and filter cake remains to handle in next step.
2. washing: the filter cake being obtained by filtration enters six rinsing bowls by 1# screw conveyor, pre- in six wash water kettles
The wash water that last time washing is added in five wash water pumps is first passed through, starts agitator treating 30 minutes, slurries are pumped into six rinsing bowls
The filtering of 2# horizontal spiral filter, filter cake enter five rinsing bowls by 2# screw conveyor, and filtrate enters six wash water slots, washes
Water is pumped into recovery process by six wash waters；Secondary wash water is added by secondary wash water pump in advance in five rinsing bowls, starts stirring,
Filter cake washs 30 minutes after entering, and slurries are pumped into 3# horizontal spiral filter with five rinsing bowls and filter, and filter cake passes through 3# spiral shell
It revolves conveyer and enters four rinsing bowls, filtrate enters the washing lotion that five wash water slots are used as six rinsing bowls；It is pre- in four rinsing bowls
Wash water is first added, starts stirring, the material washing by soaking sent by 3# screw conveyor 3 hours, slurries are pumped with four rinsing bowls
It is sent into the filtering of 4# horizontal spiral filter, filter cake enters rinsing bowl three times by 4# screw conveyor, and filtrate enters four wash waters
Slot, wash water are pumped into sewage treatment process by four wash waters；A water is previously added in rinsing bowl three times to open after filter cake is added
Dynamic stirring, is washed about 30 minutes, and slurries are pumped into 5# horizontal spiral filter with rinsing bowl three times and filter, and filter cake passes through 5# spiral
Conveyer enters secondary rinsing bowl, and filtrate is into wash water slot, wash water are pumped into solvent recovery destructive distillation slot by wash water three times three times；Two
It is previously added the primary wash liquor come by once washing pumping in secondary rinsing bowl and starts stirring after filter cake is added, washing 30 minutes,
Slurries are pumped into the filtering of 6# horizontal spiral filter with secondary rinsing bowl, and filter cake enters primary washing by 6# screw conveyor
Slot, filtrate enter secondary wash water slot, and wash water is pumped into five rinsing bowls by secondary wash water as cleaning solution；In rinsing bowl
It is previously added deionized water, after filter cake is added, starts stirring, washing 30 minutes, it is horizontal that slurries with a rinsing bowl are pumped into 7#
Spiral filter filtering, filter cake enter fluidized bed by 8# screw conveyor and are dried, and filtrate enters a wash water slot and continues to employ.
3. dry, packaging: the filter cake being obtained by filtration after primary washing, which enters fluidized bed by 8# screw conveyor, to be done
Dry, the resin after drying is directly entered the sending warehouse of flow delivery systems, packaging feed bin is transported to by air-flow, by packing automatically
And polyphenylene sulfide finished product can be obtained in packaging, tail gas empties after deduster purifies.
The mass content of sodium chloride is 10% in six wash waters in six rinsing bowls, is passed through salt recovery process, is used for back
The sodium chloride in six wash waters is received, specific operation process is precipitated crystal by being dehydrated concentration, then is realized admittedly by way of filtering
Liquid separation, filtrate therein return at dehydration concentration and are further concentrated, and filter cake is using the raw salt water washing of saturation, then passes through centrifugation
Machine centrifugal dehydration, last dry packing can be obtained the sodium chloride of recycling, and the purity of the sodium chloride of recycling is up to 99% or more.
Sewage treatment process adds low-molecular weight polymer after water to be precipitated, through filtering for handling destructive distillation slot cleaning solution for removing residue
Filter cake afterwards spontaneously dries the by-product that additive and low-grade resin alloy ingredient as other various low-grade resins can be obtained
Product, filtrate after filtering are discharged after detection is up to standard, qualified by aeration, biodegrade, precipitation process.
Embodiment 2
It according to operating procedure described in embodiment 1, is repeated 3 times, the average molecular weight difference of polyphenylene sulfide made from 3 times
Are as follows: 25880,25650,25850, molecular weight is high and relatively stable, illustrates that this method stability is good, reproducibility is high, thoroughly solves
Traditional handicraft product is unstable, molecular weight is not high problem；The quality of final obtained polyphenylene sulfide be respectively as follows: 60.3Kg,
61.2Kg, 60.4Kg, theoretical yield 72.070Kg, the yield of 3 repetitive operations is most down to 83.67%, high conversion rate.
Measure the physical property such as table 1 of polyphenylene sulfide made from 3 repetitive operations:
The physical property of 1 polyphenylene sulfide of table
As shown in Table 1, the good mechanical performance of the polyphenylene sulfide of the method for the present invention preparation, repeatability are high.
It is as described above the embodiment of the present invention.The present invention is not limited to the above-described embodiments, anyone should learn that
The structure change made under the inspiration of the present invention, the technical schemes that are same or similar to the present invention each fall within this
Within the protection scope of invention.
Claims (6)
1. a kind of preparation method of low cost polyphenylene sulfide is with N-Methyl pyrrolidone using vulcanized sodium, paracide as raw material
Solvent, it is characterised in that: using sodium benzoate, caprolactone as catalyst, using sodium hydroxide as auxiliary agent, participate in each component of reaction
Molfraction is respectively as follows: vulcanized sodium 1.0-1.5, paracide 1.0-1.6, sodium benzoate 0.05-0.15, caprolactone 0.05-
0.15, the molfraction of sodium hydroxide 0.05-0.5, solvent N-methyl pyrilidone additional amount and paracide input amount is 5-
10, raw material is added dropwise to reaction system by several times under normal pressure；Its concrete technology flow process produced includes the following steps:
(1) vulcanized sodium feeds intake: vulcanized sodium, sodium hydroxide successively being put into dehydrating kettle, add N-Methyl pyrrolidone, then
It is passed through nitrogen protection, stirring is opened, which is risen to 130-200 DEG C and is maintained；
(2) dissolution of paracide: paracide is put into paracide dissolution kettle, and N-Methyl pyrrolidone is added, starts
Stirring, under the protection of nitrogen, rises to 70-150 DEG C for the system temperature, until paracide is dissolved in N-Methyl pyrrolidone
In；
(3) dissolution of catalyst: N-Methyl pyrrolidone is first added in catalyst dissolution kettle, then puts into catalyst, then leads to
Enter nitrogen protection, start stirring, which, which is risen to 70-150 DEG C, is dissolved in catalyst in N-Methyl pyrrolidone；
(4) 1/3-1/2 for the liquor capacity that step (2) are prepared and step (3) solution prepared prepolymerization: are delivered to step
(1) in dehydrating kettle, it is passed through nitrogen protection, opens stirring, which is maintained at 130-200 DEG C, is reacted 2-4 hours,
Period is to the discharge liquor and gas progress analysis detection in reaction；
(5) it polymerize again: is passed through nitrogen protection, opens stirring, the prepolymerization liquid that step (4) obtains is delivered to polymeric kettle
It is interior, the system temperature is first down to 120-170 DEG C, the remaining part for the solution that step (2) are prepared then is delivered to polymeric kettle
It is interior, then the system temperature is maintained at 180-280 DEG C, 5-10 hour is reacted, after reaction, by the mixture in polymeric kettle
It is put into spraying seperator, using being centrifugated into polyphenylene sulfide particle；
(6) it is filtered, washed, dries, being packaged to be polyphenylene sulfide product.
2. a kind of preparation method of inexpensive polyphenylene sulfide as described in claim 1, it is characterised in that: step (1)-step
(5) tail gas that displacement nitrogen generates in, which enters after exhaust gas processing device removes pernicious gas, to be vented.
3. a kind of preparation method of inexpensive polyphenylene sulfide as described in claim 1, it is characterised in that: the dehydration of step (1)
Gaseous substance formed in kettle enters condenser through the top duct of dehydrating kettle, and condensed liquid enters condensate tank,
It is sent to recovery process recycling N-Methyl pyrrolidone, condensed remnants tail gas enters exhaust gas processing device after decompression
It is vented after removing pernicious gas.
4. a kind of preparation method of inexpensive polyphenylene sulfide as claimed in claim 3, it is characterised in that: the recovery process packet
Include following steps:
(1) wash water and the recycling of by-product salt: carrying out in dehydrating tower, and the gas after evaporation, which enters, is condensed into water in overhead condenser,
To dehydrating tower, partial condensation water is delivered in storage tank partial reflux；Tower bottom liquid after evaporation is to contain by-product salt and impure
N-Methyl pyrrolidone send to equipment for separating liquid from solid and is separated by solid-liquid separation, isolated solid be by-product salt, by-product salt send to
Drying machine is dry；
(2) N-Methyl pyrrolidone recycles: in the isolated liquid of step (1), it is delivered to N-Methyl pyrrolidone recovery tower,
By tower bottom reboiler heat temperature raising, the gas after evaporation, which enters in overhead condenser, is condensed into liquid N-Methyl pyrrolidone,
To N-Methyl pyrrolidone recovery tower, part N-Methyl pyrrolidone is delivered in storage tank partial reflux.
5. a kind of preparation method of inexpensive polyphenylene sulfide as described in claim 1, it is characterised in that: the dehydration of step (4)
Gaseous substance formed in kettle and the polymeric kettle of step (5) enters condenser through the top duct of dehydrating kettle or polymeric kettle,
Condensed liquid enters condensate tank, is sent to recovery process, and condensed remnants tail gas enters tail after decompression
Gas recovering device is vented after removing pernicious gas.
6. a kind of preparation method of inexpensive polyphenylene sulfide as described in claim 1, it is characterised in that: step (6) tool
Gymnastics is made as follows:
(1) it filters: solidliquid mixture obtained in spraying seperator is sent with the filtering of 1# horizontal spiral filter, filtrate is pumped to
Enter recovery process recycling design, filter cake remains to handle in next step；
(2) wash: the filter cake being obtained by filtration enters six rinsing bowls by 1# screw conveyor, leads in advance in six wash water kettles
The wash water that last time washing is added in five wash water pumps is crossed, starts agitator treating 20-40 minutes, slurries are pumped into 2# with six rinsing bowls
The filtering of horizontal spiral filter, filter cake enter five rinsing bowls by 2# screw conveyor, and filtrate enters six wash water slots, wash water
Recovery process is pumped by six wash waters；Secondary wash water is added by secondary wash water pump in advance in five rinsing bowls, starts stirring, is filtered
Cake washs 20-40 minutes after entering, and slurries are pumped into 3# horizontal spiral filter with five rinsing bowls and filter, and filter cake passes through 3# spiral shell
It revolves conveyer and enters four rinsing bowls, filtrate enters the washing lotion that five wash water slots are used as six rinsing bowls；It is pre- in four rinsing bowls
Wash water is first added, starts stirring, the material washing by soaking sent by 3# screw conveyor 3-4 hours, four rinsing bowls of slurries
It is pumped into the filtering of 4# horizontal spiral filter, filter cake enters rinsing bowl three times by 4# screw conveyor, and filtrate, which enters four times, washes
Sink, wash water are pumped into sewage treatment process by four wash waters；A water is previously added in rinsing bowl three times, after filter cake is added,
Stirring is started, is washed 30 minutes, slurries are pumped into 5# horizontal spiral filter with rinsing bowl three times and filter, and filter cake passes through 5# spiral
Conveyer enters secondary rinsing bowl, and filtrate is into wash water slot, wash water are pumped into solvent recovery destructive distillation slot by wash water three times three times；Two
It is previously added the primary wash liquor come by once washing pumping in secondary rinsing bowl and starts stirring after filter cake is added, washs 20-40 and divides
Clock, slurries are pumped into 6# horizontal spiral filter with secondary rinsing bowl and filter, and filter cake enters a water by 6# screw conveyor
Washing trough, filtrate enter secondary wash water slot, and wash water is pumped into five rinsing bowls by secondary wash water as cleaning solution；Rinsing bowl
In be previously added deionized water, after filter cake is added, start stirring, washing 20-40 minutes, slurries are pumped into 7# with a rinsing bowl
The filtering of horizontal spiral filter, filter cake enter fluidized bed by 8# screw conveyor and are dried, and filtrate enters a wash water slot
Continue to employ；
(3) dry, packaging: the filter cake being obtained by filtration after primary washing enters fluidized bed by 8# screw conveyor and is dried,
Resin after drying is directly entered the sending warehouse of flow delivery systems, packaging feed bin is transported to by air-flow, by packing automatically i.e.
Packaging becomes finished product, and tail gas empties after deduster purifies.
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| CN107936250B (en) * | 2017-11-29 | 2020-06-16 | 中国石油化工股份有限公司 | Method for recycling polyphenylene sulfide oligomer |
| CN108530629B (en) * | 2018-03-23 | 2020-10-20 | 四川理工学院 | Method for conveying sodium sulfide in fluidized state in pps production |
| CN110105573B (en) * | 2019-05-21 | 2022-03-08 | 中国石油化工股份有限公司 | Method for reducing COD (chemical oxygen demand) of polyphenylene sulfide byproduct salt |
| CN111004393A (en) * | 2019-12-17 | 2020-04-14 | 重庆聚狮新材料科技有限公司 | Washing water circulation process for polyphenylene sulfide production |
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| DE19623706A1 (en) * | 1996-06-14 | 1997-12-18 | Hoechst Ag | Process for the production of sulfur-containing polymers |
| JP2002293939A (en) * | 2001-03-30 | 2002-10-09 | Petroleum Energy Center | Method for polyarylene sulfide production |
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