CN106750299A - A kind of preparation method of inexpensive polyphenylene sulfide - Google Patents
A kind of preparation method of inexpensive polyphenylene sulfide Download PDFInfo
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- CN106750299A CN106750299A CN201710026395.6A CN201710026395A CN106750299A CN 106750299 A CN106750299 A CN 106750299A CN 201710026395 A CN201710026395 A CN 201710026395A CN 106750299 A CN106750299 A CN 106750299A
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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
- C08G75/0254—Preparatory processes using metal sulfides
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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
- C08G75/0277—Post-polymerisation treatment
- C08G75/0281—Recovery or purification
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Abstract
The invention discloses a kind of preparation method of inexpensive polyphenylene sulfide,It is related to polymeric material field,With vulcanized sodium,Paracide is raw material,With Sodium Benzoate,Caprolactone is catalyst,With N methyl pyrrolidones as solvent,With NaOH as auxiliary agent,The concrete technology flow process of its production feeds intake including vulcanized sodium successively,Paracide feeds intake,The dissolving of catalyst,Prepolymerization,It is polymerized again,Filtering,Washing,Dry,Packing department,Finally give polyphenylene sulfide product,The present invention has abandoned the chlorination lithium catalyst that existing domestic prevailing technology is used,Sodium Benzoate and caprolactone with low cost are catalyst,Reduce production cost,The method that all raw materials are added dropwise by several times using normal pressure,Polymerisation is set to be carried out in certain temperature range,Heat release implode when effectively prevent polymerisation,Improve the degree of polymerization and various mechanical performances of polyphenylene sulfide,Thoroughly solve traditional handicraft product unstable,Molecular weight is not high,The problem of poor performance.
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 technology
Polyphenylene sulfide has excellent heat endurance, chemical stability, corrosion resistance and an electrical property, and inorganic is filled out with various
Material has good compatibility, can be compound with various inorganic fillers and other macromolecular materials, is made the engineering of various excellent performances
Plastics and blend alloy.Additionally, the dimensional stability of polyphenylene sulfide (PPS) product is protruded, can be added using almost all of plastics
Work method is processed, and including spraying, injection, compression moulding, extrusion, blowing and embedding etc., also can carry out secondary operation to product.Cause
This, polyphenylene sulfide (PPS) has at aspects such as automobile making, electric, machine-building, chemical industry instrument and meter and aerospace industries
It is widely applied, is described as the sixth-largest engineering plastics, exploitation prospect is very wide.
The synthetic method of current polyphenylene sulfide has：
1st, sodium sulfide method.PPS is obtained by condensation reaction in polar solvent with paracide and anhydrous sodium sulfide.The method
It is that, with anhydrous sodium sulfide and Isosorbide-5-Nitrae-dichloro-benzenes as raw material, alkali metal salt reacts polycondensation as auxiliary agent in highly polar proton solvent
Prepare PPS.
2nd, sulfur solution route.It is the distinctive synthesis polyphenylene sulfide process route of China, this method practicality sulphur replaces vulcanized sodium
As sulphur source, in the range of 175-250 DEG C, using paracide and sulphur as raw material, metal and low valence metal ion salt and have
Machine acids etc. makees catalyst, polycondensation reaction occurs under normal pressure in polar solvent and prepares PPS, and it is crucial that sulfur solution route prepares PPS
It is the fracture of the ring of sulphur eight, the generation of sulphur anion.
3rd, hydrogen sulfide method.The method adds a certain amount of tertiary sodium phosphate with hydrogen sulfide, NaOH and paracide as raw material
Make auxiliary agent, normal pressure polycondensation reaction is carried out in polar solvent hexamethylphosphorictriamide (HMPA).
4th, oxidation polymerization route.The method is that, as raw material, oxygen or air are oxidant, second with Diphenyl disulfide ether (DSP)
Sour acetone oxidation vanadium or Lewis acid are catalyst, react PPS is obtained at normal temperatures and pressures.
5th, to halo benzenethiol salt from polycondensation route.To halo benzenethiol, halogenated methyl benzenethiol, many phenylene sulphur of halo
The alkali metal salt of phenol, and these salt are by the derivative after alkyl, aromatic core substitution base substitution, in N2Can be carried out with the presence of pyridine
Itself polycondensation.
The problem that above technology is present is respectively：
1st, it is catalyst to use lithium chloride, increased production cost.
2nd, synthesis PPS molecular weight is high, lot stability is bad.
3rd, synthesis condition is harsh, and equipment is complicated, relatively costly, manufactures high energy consumption.
The Phillips Petroleum Company in the U.S. develops the Industrialized synthesis method of PPS in the seventies of twentieth century six,
The said firm proposes with vulcanized sodium and paracide as raw material that METHYLPYRROLIDONE is solvent for the first time, through dehydration and
Polycondensation process obtains fusing point and is more than 275 DEG C of PPS resin, and realizes the industrialized production of PPS first in 1971, in morning
Phase, the molecular weight product produced with the method is relatively low (weight average molecular weight is less than 2 × 104), thus shock resistance is poor；And by
In the presence of inorganic salts, the moisture-proof of product, mouldability are also poor.To reduce the mobility of resin to meet process requirements,
The early stage production of PPS generally improves molecular weight by oxidation cross-linked mode.
In the United States Patent (USP) of Patent No. US4728231, for the technological improvement that the relatively low problem of molecular weight product is proposed
Method is：By adding alkali metal carboxylate and water reaction chain extension in polyphenylene sulfide is melted, then polyphenylene sulfide is separated out so as to increase
Plus molecular weight, but this reaction is carried out under high-temperature and high-pressure conditions, and condition is harsh, and equipment is complicated, relatively costly.
Japanese Kureha Kagaku Kogyo K.K. has also applied for substantial amounts of Japan to the PPS resin synthesis technique of different performance
Patent is (such as:JP 62-253626, JP 2004-24619).Indentation course of reaction is generally using the method for second-stage reaction
To obtain satisfactory PPS resin, the said firm also refer to similar PPS in the patent CN88108247.3 of China's application
Synthetic technology of resins, but manufacture energy consumption to PPS do not illustrate accordingly, in actual production, produces also certain in the method
There is a problem of manufacturing high energy consumption.
China starts to study the synthesis of PPS resin with application in 20 century 70s, and correlative study is looked forward to production
Industry has also applied for some Chinese patents (such as CN85102554A, CN00116141.5, CN1793202A, CN104877167).
At present, domestic main PPS manufacturers are that Honghe Chemical Industry Co. Ltd. Zigong, Zhejiang newly synthesize the limited public affairs of special material
Department etc..It is catalyst that Chinese PPS synthesis mostly use lithium chloride, but with the rising of lithium chloride cost in recent years, causes to produce
Cost increases, and urgent need finds cheap catalyst and substitutes.And synthesis PPS molecular weight is high, lot stability is difficult to control to.
The content of the invention
The present invention provides a kind of preparation method of inexpensive polyphenylene sulfide, it is to avoid use lithium chloride, reduces into product cost, with
Solve prior art synthesis PPS molecular weight it is not high, lot stability is bad, synthesis condition is harsh, equipment is complicated, relatively costly
And the problem of manufacture high energy consumption.
To solve above-mentioned technical problem, the present invention uses following technical scheme：
A kind of preparation method of inexpensive polyphenylene sulfide, with vulcanized sodium, paracide as raw material, with 1-METHYLPYRROLIDONE
It is solvent, with Sodium Benzoate, caprolactone as catalyst, with NaOH as auxiliary agent, the concrete technology flow process of its production is included such as
Lower step：
(1) vulcanized sodium feeds intake：During vulcanized sodium, NaOH put into dehydrating kettle successively, 1-METHYLPYRROLIDONE is added,
Nitrogen protection is then passed to, stirring is opened, the system temperature is risen to 130-200 DEG C and is maintained；
(2) dissolving of paracide：By in paracide input paracide dissolution kettle, 1-METHYLPYRROLIDONE is added,
Stirring is started, under the protection of nitrogen, the system temperature 70-150 DEG C is risen to, until paracide is dissolved in N- methylpyrroles
In alkanone；
(3) dissolving of catalyst：1-METHYLPYRROLIDONE is first added in catalyst dissolution kettle, then puts into catalyst, so
After be passed through nitrogen protection, start stirring, the system temperature is risen into 70-150 DEG C makes catalyst dissolution in 1-METHYLPYRROLIDONE
In；
(4) prepolymerization：The solution that the 1/3-1/2 and step (3) of the liquor capacity that step (2) is prepared are prepared is delivered to
In the dehydrating kettle of step (1), nitrogen protection is passed through, opens stirring, the system temperature is maintained at 130-200 DEG C, 2-4 is small for reaction
When, period is analyzed detection to the discharge liquor and gas in reaction；
(5) it is polymerized again：Nitrogen protection is passed through, stirring is opened, the prepolymerization liquid that step (4) is obtained is delivered to polymerization
In kettle, the system temperature is first down to 120-170 DEG C, the remaining part of the solution for then preparing step (2) is delivered to polymerization
In kettle, then the system temperature is maintained at 180-280 DEG C, reacted 5-10 hour, after reaction terminates, by the mixing in polymeric kettle
Thing is put into spraying seperator, using being centrifugated into polyphenylene sulfide particle；
(6) filter, wash, dry, be packaged to be polyphenylene sulfide product.
Preferably, the molfraction for participating in each component of reaction is respectively：
Vulcanized sodium 1.0-1.5, paracide 1.0-1.6, Sodium Benzoate 0.05-0.15, caprolactone 0.05-0.15, hydrogen-oxygen
Change sodium 0.05-0.5, solvent N-methyl pyrilidone addition is 5-10 with the molfraction of paracide input amount.
Preferably, the tail gas that displacement nitrogen is produced in step (1)-step (5) enters exhaust gas processing device and removes harmful gas
It is vented after body.Preferably, the gaseous substance formed in the dehydrating kettle of step (1) enters condensation through the top duct of dehydrating kettle
Device, condensed liquid enters condensate tank, is sent to solvent recovery operation and reclaims 1-METHYLPYRROLIDONE, condensed
Remaining tail gas is vented by entering after decompression after exhaust gas processing device removes pernicious gas.
Preferably, the recovery process comprises the following steps：
(1) wash water and by-product salt are reclaimed：Carried out in dehydrating tower, the gas after evaporation is into being condensed into overhead condenser
Water, partial reflux to dehydrating tower, partial condensation water is delivered in storage tank；Tower bottom liquid after evaporation is containing by-product salt and impure
1-METHYLPYRROLIDONE, delivering to equipment for separating liquid from solid carries out separation of solid and liquid, and isolated solid is by-product salt, and by-product salt send
Dried to drying machine；
(2) 1-METHYLPYRROLIDONE is reclaimed：In the isolated liquid of step (1), it is delivered to 1-METHYLPYRROLIDONE and returns
Tower is received, by tower bottom reboiler heat temperature raising, gas after evaporation is into being condensed into liquid N- methylpyrroles in overhead condenser
Alkanone, partial reflux to de- 1-METHYLPYRROLIDONE tower, part 1-METHYLPYRROLIDONE is delivered in storage tank.
Preferably, the gaseous substance formed in the polymeric kettle of the dehydrating kettle of step (4) and 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 is returned
Sequence of knocking off recycling design and catalyst, condensed remaining tail gas remove pernicious gas by entering exhaust gas processing device after decompression
After be vented.
Preferably, the step (6) concrete operations are as follows：
(1) filter：The solidliquid mixture obtained in seperator of spraying is filtered with 1# horizontal spirals filter is pumped to, filter
Liquid sends into solvent and catalyst recovery process recycling design and catalyst, and filter cake remains next step treatment；
(2) wash：The filter cake being filtrated to get enters six rinsing bowls by 1# conveying worms, pre- in six wash water kettles
Five wash waters of wash water pump addition last time washing are first passed through, is started agitator treating 20-40 minutes, slurries are pumped with six rinsing bowls
Enter the filtering of 2# horizontal spirals filter, filter cake enters five rinsing bowls by 2# conveying worms, and filtrate enters six wash water grooves,
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, is started and is stirred
Mix, filter cake is washed 20-40 minutes after entering, slurries are pumped into 3# horizontal spirals filter and filter with five rinsing bowls, and filter cake leads to
3# conveying worms into four rinsing bowls are crossed, filtrate enters five wash water grooves and is used as six washing lotions of rinsing bowl；Four washings
Wash water is previously added in groove, stirring is started, the material washing by soaking sent by 3# conveying worms 3-4 hours, slurries are with four times
Rinsing bowl is pumped into the filtering of 4# horizontal spirals filter, and filter cake enters three rinsing bowls by 4# conveying worms, and filtrate enters
Four wash water grooves, wash water is pumped into sewage disposal operation by four wash waters；A water is previously added in three rinsing bowls, filter cake adds
After entering, stirring is started, washed about 30 minutes, slurries are pumped into 5# horizontal spirals filter and filter with three rinsing bowls, and filter cake leads to
5# conveying worms into secondary rinsing bowl are crossed, filtrate enters three wash water grooves, and wash water is pumped into solvent recovery by three wash waters
Destructive distillation groove；It is previously added in secondary rinsing bowl by once washing the primary wash liquor that pumping comes, after filter cake is added, starts stirring, is washed
Wash 20-40 minutes, the secondary rinsing bowl of slurries is pumped into the filtering of 6# horizontal spirals filter, filter cake is entered by 6# conveying worms
Enter a rinsing bowl, filtrate enters secondary wash water groove, wash water is pumped into five rinsing bowls as cleaning solution by secondary wash water；One
It is previously added deionized water in secondary rinsing bowl, after filter cake is added, starts stirring, washing 20-40 minutes, slurries are with a rinsing bowl
The filtering of 7# horizontal spirals filter is pumped into, filter cake enters fluidized bed and is dried by 8# conveying worms, and filtrate enters one
Secondary wash water groove is continued to employ；
(3) dry, pack：The filter cake being filtrated to get after once washing enters fluidized bed by 8# conveying worms to be done
Dry, dried resin is directly entered the sending warehouse of flow delivery systems, and packaging feed bin is transported to by air-flow, by packing automatically
And packaging turns into finished product, is emptied after the purification of tail gas removing dust device.
Preferably, mass content is the sodium chloride of 8-15% during the recovery process is used to reclaim washings, is passed sequentially through
Dehydration, separation, the washing of raw salt, centrifugal dehydration, dry packing operation.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention has abandoned existing domestic prevailing technology and has used on the basis of conventional vulcanized sodium method production PPS resin
Chlorination lithium catalyst, with low cost Sodium Benzoate and caprolactone be catalyst, prepare capability and performance stabilization and cost
Relatively low polyphenylene sulfide, ten thousand/tons of chlorination lithium catalyst present price 12-15 sale that prevailing technology is used domestic at present
Valency, accounts for cost of material 30-37.5%, uses the PPS high costs of the produced in conventional processes of lithium chloride, uncontested advantage, state expert
Industry is in be lost and profit edge, and uses the Sodium Benzoate and caprolactone mixed catalyst of factory formula of the present invention and low cost
Technological process can then save the cost of ten thousand yuan/ton of 2-3, and the superior product quality of output, price are low；
(2) method that all raw materials of the invention are added dropwise by several times using normal pressure, makes polymerisation enter in certain temperature range
OK, heat release implode when effectively prevent polymerisation, improves the degree of polymerization and various mechanical performances of polyphenylene sulfide, the method
Good stability, reappearance are high, thoroughly solve the problems, such as that traditional handicraft product is unstable, molecular weight is not high, poor performance；
(3) energy resource consumption of the present invention is low, and the Sodium Benzoate and caprolactone using factory formula of the present invention and low cost mix
After the process route of catalyst, the synthesizing section cycle reduces, and auxiliary agent recovery process is more simple, energy consumption reduction, three waste discharge
Greatly reduce.
Specific embodiment
Application principle of the invention, effect and effect, are explained by the way that mode is implemented as follows.
Embodiment 1
Before delivering production, purity first is carried out to paracide, vulcanized sodium, 1-METHYLPYRROLIDONE, NaOH, catalyst
Analysis, to avoid the influence later stage from producing.
By taking the injected volume of 100Kg paracide as an example, proceed as follows：
(1) vulcanized sodium feeds intake：
The air bleeding valve for leading to exhaust gas processing device of dehydrating kettle was first opened before charging, the pressure in dehydrating kettle is released
Put.
The whole bag sheet technical pure vulcanized sodium of 52Kg is transported to dehydration workshop, elevator by dolly in storehouse
The floor to where between unpacking is carried, between being transported to the unpacking of closed ventilation, vulcanized sodium is unpacked and is put into feed hopper, while adding
, be discharged into dehydrating kettle for vulcanized sodium and NaOH by feed hopper by 2.5kg NaOH；
N- first is sent into from the 1-METHYLPYRROLIDONE measuring tank that 1-METHYLPYRROLIDONE pump flows back from solvent storage tank to band
Base pyrrolidones, from 1-METHYLPYRROLIDONE measuring tank to the 1-METHYLPYRROLIDONE that 300kg is added in dehydrating kettle；Simultaneously with N-
Methyl pyrrolidone (in self-measuring groove) is flushed into hopper, makes vulcanized sodium and NaOH completely into dehydrating kettle, is passed through nitrogen
Gas excludes air in kettle, starts stirring, under the protection of nitrogen, 130- is progressively warming up to mixture by the steam in chuck
200℃。
Gaseous substance formed in this step operation process enters condenser, and condensed liquid is stored up into condensate liquid
Tank, recovery process recovery 1-METHYLPYRROLIDONE is sent to 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) dissolving of paracide：
The air bleeding valve that dissolution kettle leads to tail gas absorber was first opened before charging, the pressure in dissolution kettle is discharged.
The whole bag paracide of 100Kg in storehouse is transported to dehydration workshop by dolly, elevator is carried to unpacking
Between where floor, between being transported to the unpacking of closed ventilation, paracide is unpacked and is put into feed hopper, will be to two by feed hopper
Chlorobenzene is discharged into dissolution kettle；
The dissolving 1-METHYLPYRROLIDONE measuring tank feeding flowed back from solvent storage tank to band from 1-METHYLPYRROLIDONE pump
1-METHYLPYRROLIDONE, from dissolving 1-METHYLPYRROLIDONE measuring tank to the 1-METHYLPYRROLIDONE that 50kg is added in dissolution kettle；
Hopper is flushed into 1-METHYLPYRROLIDONE (in self-measuring groove) simultaneously, makes paracide completely into dissolution kettle, be passed through nitrogen
Gas excludes air in kettle, and remaining tail gas enters tail gas washing tower and removes emptying after pernicious gas, stirring is started, in the protection of nitrogen
Under, 150 DEG C are progressively warming up to mixture by the steam in chuck, paracide is dissolved in 1-METHYLPYRROLIDONE.
(3) dissolving of catalyst
With 1-METHYLPYRROLIDONE pump to the 1-METHYLPYRROLIDONE that 100kg is added in catalyst dissolution kettle, it is catalyzed in dress
The air bleeding valve that catalyst dissolution kettle leads to tail gas absorber is first opened before agent, the pressure in catalyst dissolution kettle is discharged；It is logical
Too small hopper to 8Kg Sodium Benzoates and 8Kg caprolactones is added in catalyst dissolution kettle, and with the N- crassitudes of 10kg or so
Ketone rinses hopper, closes charging.
Again to the 1-METHYLPYRROLIDONE that 100kg is added in catalyst dissolution kettle, valve is closed, be passed through nitrogen, replace nitrogen
Tail gas after gas behind absorption tower by being vented；Nitrogen valve is closed, is heated by jacket steam, make catalyst dissolution.
(4) prepolymerization
The complete soln pump that the solution and step (3) that 60kg steps (2) are prepared are prepared is delivered in step (1)
Dehydrating kettle, under the protection of nitrogen, stirring is started, and 180~200 DEG C are maintained at by jacket steam heating-up temperature, and reaction 2 is small
When, carry out prepolymerization.
Period is analyzed detection to the discharge liquor and gas in reaction, to determine prepolymerized process.
During this step operation
The gaseous substance for being formed enters condenser, and condensed liquid enters condensate tank, is sent to reclaim work
Sequence recycling design and catalyst, remaining tail gas are put after depressurizing and removing the pernicious gases such as hydrogen sulfide into exhaust gas processing device
It is empty.
(5) it is polymerized again
Polymeric kettle stirring is started, air in polymeric kettle is replaced with nitrogen, tail gas is emptied by tail gas washing tower；Step
(5) the pre-polymer solution pump for obtaining 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, are delivered in polymeric kettle remaining 90kg paracide -1-METHYLPYRROLIDONE solution with pump, chuck
Continue logical cooling water or steam, temperature control in polymeric kettle at 180~200 DEG C, is reacted 6 hours.
After reaction terminates, mixture in reactor is put into spraying seperator, using being centrifugated into polyphenylene sulfide
Grain.
Gaseous substance formed in this step operation process enters condenser, and condensed liquid is stored up into condensate liquid
Tank, is sent to recovery process recycling design and catalyst, and remaining tail gas enters tail gas washing tower and removes hydrogen sulfide by decompression
It is vented Deng after pernicious gas.
(6) filtering, washing, dry, packaging process：
1. filter：The solidliquid mixture obtained in seperator of spraying is filtered with 1# horizontal spirals filter is pumped to, filter
Liquid sends into solvent and catalyst recovery process recycling design and catalyst, and filter cake remains next step treatment.
2. wash：The filter cake being filtrated to get enters six rinsing bowls by 1# conveying worms, pre- in six wash water kettles
Five wash waters of wash water pump addition last time washing are first passed through, agitator treating is started 30 minutes, slurries are pumped into six rinsing bowls
2# horizontal spirals filter is filtered, and filter cake enters five rinsing bowls by 2# conveying worms, and filtrate enters six wash water grooves, 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, stirring is started,
Filter cake is washed 30 minutes after entering, and slurries are pumped into 3# horizontal spirals filter and filter with five rinsing bowls, and filter cake passes through 3# spiral shells
Rotation conveyer enters four rinsing bowls, and filtrate enters five wash water grooves and is used as six washing lotions of rinsing bowl；It is pre- in four rinsing bowls
Wash water is first added, stirring is started, the material washing by soaking sent by 3# conveying worms 3 hours, slurries are with four rinsing bowl pumps
Feeding 4# horizontal spirals filter filtering, filter cake enters three rinsing bowls by 4# conveying worms, and filtrate enters four wash waters
Groove, wash water is pumped into sewage disposal operation by four wash waters；A water is previously added in three rinsing bowls, after filter cake is added, is opened
Dynamic stirring, washs about 30 minutes, and slurries are pumped into 5# horizontal spirals filter and filter with three rinsing bowls, and filter cake passes through 5# spirals
Conveyer enters secondary rinsing bowl, and filtrate enters three wash water grooves, and wash water is pumped into solvent recovery destructive distillation groove by three wash waters；Two
It is previously added in secondary rinsing bowl by once washing the primary wash liquor that pumping comes, after filter cake is added, starts stirring, is washed 30 minutes,
The secondary rinsing bowl of slurries is pumped into the filtering of 6# horizontal spirals filter, and filter cake is entered by 6# conveying worms once to be washed
Groove, filtrate enters secondary wash water groove, and wash water is pumped into five rinsing bowls as cleaning solution by secondary wash water；In rinsing bowl
It is previously added deionized water, after filter cake is added, starts stirring, washing 30 minutes, it is horizontal that rinsing bowl of slurries is pumped into 7#
Spiral filter is filtered, and filter cake enters fluidized bed and is dried by 8# conveying worms, and filtrate is continued to employ into a wash water groove.
3. dry, pack：The filter cake being filtrated to get after once washing enters fluidized bed by 8# conveying worms to be done
Dry, dried resin is directly entered the sending warehouse of flow delivery systems, and packaging feed bin is transported to by air-flow, by packing automatically
And packaging can obtain polyphenylene sulfide finished product, be emptied after the purification of tail gas removing dust device.
The mass content of sodium chloride is 10% in six wash waters in six rinsing bowls, is passed through salt recovery process, for returning
The sodium chloride in six wash waters is received, specific operation process separates out crystal by being dehydrated concentration, then is realized by way of filtering solid
Liquid is separated, and filtrate therein returns to and further concentrated at dehydration concentration, and filter cake uses the raw salt water washing of saturation, then by centrifugation
Machine centrifugal dehydration, last dry packing can the sodium chloride that be recycled, the purity of the sodium chloride of recovery is up to more than 99%.
Sewage disposal operation is used to process destructive distillation groove cleaning solution for removing residue, and low-molecular weight polymer is separated out after adding water, through filtering
Filter cake afterwards spontaneously dries the by-product of the additive and low-grade resin alloy composition that can obtain being used as other various low-grade resins
Product, filtrate after filtering is by aeration, biodegradable, precipitation operation, discharge after detection is up to standard, qualified.
Embodiment 2
According to the operating procedure described in embodiment 1, it is repeated 3 times, the mean molecule quantity difference of polyphenylene sulfide obtained in 3 times
For：25880th, 25650,25850, molecular weight is high and relatively stable, illustrates that the method good stability, reappearance are high, thoroughly solves
Traditional handicraft product is unstable, molecular weight is not high problem；The quality of final obtained polyphenylene sulfide is respectively：60.3Kg、
61.2Kg, 60.4Kg, theoretical yield is 72.070Kg, and the yield for repeating for 3 times is minimum up to 83.67%, high conversion rate.
Measure the physical property such as table 1 for repeating obtained polyphenylene sulfide for 3 times：
The physical property of the polyphenylene sulfide of table 1
As shown in Table 1, the good mechanical performance of polyphenylene sulfide prepared by the inventive method, repeatability is high.
Embodiments of the invention are as described above.The present invention is not limited to the above-described embodiments, and anyone should learn
The structure change made under enlightenment of the invention, it is every with of the invention with same or like technical scheme, each fall within this
Within the protection domain of invention.
Claims (8)
1. a kind of preparation method of inexpensive polyphenylene sulfide, with vulcanized sodium, paracide as raw material, be with 1-METHYLPYRROLIDONE
Solvent, it is characterised in that：With Sodium Benzoate, caprolactone as catalyst, with NaOH as auxiliary agent, the concrete technology stream of its production
Journey comprises the following steps：
(1) vulcanized sodium feeds intake：During vulcanized sodium, NaOH put into dehydrating kettle successively, 1-METHYLPYRROLIDONE is added, then
Nitrogen protection is passed through, stirring is opened, the system temperature is risen to 130-200 DEG C and is maintained；
(2) dissolving of paracide：By in paracide input paracide dissolution kettle, 1-METHYLPYRROLIDONE is added, started
Stirring, under the protection of nitrogen, 70-150 DEG C is risen to by the system temperature, until paracide is dissolved in 1-METHYLPYRROLIDONE
In；
(3) dissolving of catalyst：1-METHYLPYRROLIDONE is first added in catalyst dissolution kettle, then puts into catalyst, Ran Houtong
Enter nitrogen protection, start stirring, the system temperature is risen into 70-150 DEG C makes catalyst dissolution in 1-METHYLPYRROLIDONE；
(4) prepolymerization：The solution that the 1/3-1/2 and step (3) of the liquor capacity that step (2) is prepared are prepared is delivered to step
(1) in dehydrating kettle, nitrogen protection is passed through, opens stirring, the system temperature is maintained at 130-200 DEG C, reacted 2-4 hours,
Period is analyzed detection to the discharge liquor and gas in reaction；
(5) it is polymerized again：Nitrogen protection is passed through, stirring is opened, the prepolymerization liquid that step (4) is obtained is delivered to polymeric kettle
It is interior, the system temperature is first down to 120-170 DEG C, the remaining part of the solution for then preparing step (2) is delivered to polymeric kettle
It is interior, then the system temperature is maintained at 180-280 DEG C, react 5-10 hour, after reaction terminates, by the mixture in polymeric kettle
It is put into spraying seperator, using being centrifugated into polyphenylene sulfide particle；
(6) filter, wash, dry, be packaged to be polyphenylene sulfide product.
2. a kind of preparation method of inexpensive polyphenylene sulfide as claimed in claim 1, it is characterised in that：Participate in each group of reaction
The molfraction divided is respectively：Vulcanized sodium 1.0-1.5, paracide 1.0-1.6, Sodium Benzoate 0.05-0.15, caprolactone
The molfraction of 0.05-0.15, NaOH 0.05-0.5, solvent N-methyl pyrilidone addition and paracide input amount
It is 5-10.
3. a kind of preparation method of inexpensive polyphenylene sulfide as claimed in claim 1 or 2, it is characterised in that：Step (1)-step
Suddenly the tail gas that displacement nitrogen is produced in (5) is vented after entering exhaust gas processing device removing pernicious gas.
4. a kind of preparation method of inexpensive polyphenylene sulfide as claimed in claim 1 or 2, it is characterised in that：Step (1) it is de-
Gaseous substance formed in water kettle enters condenser through the top duct of dehydrating kettle, and condensed liquid is stored up into condensate liquid
Tank, is sent to recovery process and reclaims 1-METHYLPYRROLIDONE, and condensed remaining tail gas is by entering vent gas treatment after decompression
Device is vented after removing pernicious gas.
5. a kind of preparation method of inexpensive polyphenylene sulfide as claimed in claim 4, it is characterised in that：The recovery process bag
Include following steps：
(1) wash water and by-product salt are reclaimed：Carried out in dehydrating tower, the gas after evaporation into being 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 containing by-product salt and impure
1-METHYLPYRROLIDONE, delivering to equipment for separating liquid from solid carries out separation of solid and liquid, and isolated solid is by-product salt, and by-product salt is delivered to
Drying machine is dried；
(2) 1-METHYLPYRROLIDONE is reclaimed：In the isolated liquid of step (1), 1-METHYLPYRROLIDONE recovery tower is delivered to,
By tower bottom reboiler heat temperature raising, gas after evaporation into being condensed into liquid 1-METHYLPYRROLIDONE in overhead condenser,
To 1-METHYLPYRROLIDONE recovery tower, part 1-METHYLPYRROLIDONE is delivered in storage tank partial reflux.
6. a kind of preparation method of inexpensive polyphenylene sulfide as claimed in claim 1 or 2, it is characterised in that：Step (4) it is de-
Gaseous substance formed in the polymeric kettle of water kettle and step (5) enters condensation through the top duct of dehydrating kettle or polymeric kettle
Device, condensed liquid enters condensate tank, is sent to recovery process, and condensed remaining tail gas after decompression by entering
Device for recovering tail gas is vented after removing pernicious gas.
7. a kind of preparation method of inexpensive polyphenylene sulfide as claimed in claim 1 or 2, it is characterised in that：The step (6)
Concrete operations are as follows：
(1) filter：The solidliquid mixture obtained in seperator of spraying is filtered with 1# horizontal spirals filter is pumped to, filtrate is sent
Enter recovery process recycling design, filter cake remains next step treatment；
(2) wash：The filter cake being filtrated to get enters six rinsing bowls by 1# conveying worms, leads in advance in six wash water kettles
Five wash waters of wash water pump addition last time washing are crossed, is started agitator treating 20-40 minutes, slurries are pumped into 2# with six rinsing bowls
Horizontal spiral filter is filtered, and filter cake enters five rinsing bowls by 2# conveying worms, and filtrate enters six wash water grooves, wash water
Recovery process is pumped into by six wash waters；Secondary wash water is added by secondary wash water pump in advance in five rinsing bowls, stirring is started, filtered
Cake is washed 20-40 minutes after entering, and slurries are pumped into 3# horizontal spirals filter and filter with five rinsing bowls, and filter cake passes through 3# spiral shells
Rotation conveyer enters four rinsing bowls, and filtrate enters five wash water grooves and is used as six washing lotions of rinsing bowl；It is pre- in four rinsing bowls
Wash water is first added, stirring is started, the material washing by soaking sent by 3# conveying worms 3-4 hours, slurries are with four rinsing bowls
The filtering of 4# horizontal spirals filter is pumped into, filter cake enters three rinsing bowls by 4# conveying worms, and filtrate is washed into four times
Tank, wash water is pumped into sewage disposal operation by four wash waters；A water is previously added in three rinsing bowls, after filter cake is added,
Stirring is started, is washed about 30 minutes, slurries are pumped into 5# horizontal spirals filter and filter with three rinsing bowls, and filter cake passes through 5# spiral shells
Rotation conveyer enters secondary rinsing bowl, and filtrate enters three wash water grooves, and wash water is pumped into solvent recovery destructive distillation groove by three wash waters；
It is previously added in secondary rinsing bowl by once washing the primary wash liquor that pumping comes, after filter cake is added, starts stirring, washs 20-40
Minute, the secondary rinsing bowl of slurries is pumped into the filtering of 6# horizontal spirals filter, and filter cake is entered once by 6# conveying worms
Rinsing bowl, filtrate enters secondary wash water groove, and wash water is pumped into five rinsing bowls as cleaning solution by secondary wash water；Once wash
Deionized water is previously added in groove, after filter cake is added, stirring is started, washed 20-40 minutes, slurries are pumped into a rinsing bowl
7# horizontal spirals filter is filtered, and filter cake enters fluidized bed and is dried by 8# conveying worms, and filtrate enters a wash water
Groove is continued to employ；
(3) dry, pack：The filter cake being filtrated to get after once washing enters fluidized bed and is dried by 8# conveying worms,
Dried resin is directly entered the sending warehouse of flow delivery systems, and packaging feed bin is transported to by air-flow, packed by automatic and
Packaging turns into finished product, is emptied after the purification of tail gas removing dust device.
8. a kind of preparation method of inexpensive polyphenylene sulfide as claimed in claim 7, it is characterised in that：The wash water and salt are returned
Mass content is the sodium chloride of 8-15% during sequence of knocking off is used to reclaim washings and washings, passes sequentially through dehydration, separation, raw salt
Washing, centrifugal dehydration, dry packing operation.
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