CN104817716B - The production method of crystal type Polymer Synthesizing method for recovering solvents and polyphenylene sulfide - Google Patents
The production method of crystal type Polymer Synthesizing method for recovering solvents and polyphenylene sulfide Download PDFInfo
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- CN104817716B CN104817716B CN201510218886.1A CN201510218886A CN104817716B CN 104817716 B CN104817716 B CN 104817716B CN 201510218886 A CN201510218886 A CN 201510218886A CN 104817716 B CN104817716 B CN 104817716B
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- 239000004734 Polyphenylene sulfide Substances 0.000 title claims abstract description 42
- 229920000069 polyphenylene sulfide Polymers 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000002904 solvent Substances 0.000 title abstract description 35
- 238000000034 method Methods 0.000 title abstract description 33
- 239000013078 crystal Substances 0.000 title abstract description 17
- 229920000642 polymer Polymers 0.000 title abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 24
- 238000004064 recycling Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000013461 design Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000009834 vaporization Methods 0.000 claims description 79
- 230000008016 vaporization Effects 0.000 claims description 79
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 230000007246 mechanism Effects 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 239000013557 residual solvent Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 239000008096 xylene Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 5
- 239000002826 coolant Substances 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000005485 electric heating Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 206010013786 Dry skin Diseases 0.000 claims description 3
- 238000012676 equilibrium polymerization Methods 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 5
- 229920002521 macromolecule Polymers 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 239000002994 raw material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000007701 flash-distillation Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 5
- 208000005156 Dehydration Diseases 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
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- 239000012065 filter cake Substances 0.000 description 2
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- 238000002347 injection Methods 0.000 description 2
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- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
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- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
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- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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Abstract
The present invention relates to the production methods of crystal type Polymer Synthesizing method for recovering solvents and polyphenylene sulfide, belong to polymeric material field.The technical problem to be solved by the present invention is to provide crystal type Polymer Synthesizing method for recovering solvents this method to include the following steps：1) after the completion of solution polymerization, reaction solution is flashed in the state of stirring, negative pressure, heating, recycling design；2) the powdered product washing after recycling design, drying are to get crystal type high molecular material.Compared with prior art, the present invention overcomes solvent recovery high energy consumption in existing crystal type Polymer production technique, loss is big the problem of, the problem of inorganic salt particle cleaning that product particle wraps up in traditional handicraft does not cause totally macromolecule product purity not high is also overcomed simultaneously, a kind of new method for recovering solvents is provided for the field of polymers, simplifies production procedure.
Description
Technical field
The present invention relates to the production methods of crystal type Polymer Synthesizing method for recovering solvents and polyphenylene sulfide, belong to macromolecule
Material Field.
Background technology
In polymeric material field, crystalline state is one of Main Morphology of macromolecular condensed state, crystalline state high molecular polymerization
The regularly arranged region of object is known as crystalline region, and disorderly arranged region is known as amorphous area, and the percentage shared by crystalline region is known as crystallinity.It is common
Crystal type high molecular material mainly have polyethylene, polystyrene, polytetrafluoroethylene (PTFE), polyphenylene sulfide etc..
Wherein, polyphenylene sulfide (PPS) is a kind of crystal type high molecular material of novel excellent combination property.In structure
On, PPS has higher intensity and modulus and good size due to having extremely intensive phenyl ring and sulphur atom on major key
Stability, also with excellent heat resistance, the cementitiousness of protrusion, electrical insulation capability and good solvent resistant and resistant to chemical etching
Performance, so ranking one of the sixth-largest special engineering plastics and " eight is big " aerospace material.PPS is widely used in aviation boat
My god, the fields such as electronic apparatus, petrochemical industry, machinery, instrument, household electrical appliance, medical instrument, automobile, anticorrosion equipment, be
Indispensable new material in the development of the national economy, particularly Hi-tech Industry Development field.
PPS resin be Philips Petroleum Co. of the U.S. (Philips Petroleum) J.Edmond and S.Hill in
Nineteen sixty-eight developed first with solution polymerization process, and this method for putting into industrialized production in 1973 is with paracide
With vulcanized sodium pressurization generation PPS is carried out in N-Methyl pyrrolidone (NMP) solution.Most of producer uses this both at home and abroad at present
Method carries out the industrialized production of PPS.
In general, using being filtered after cooling after the completion of polyphenylene sulfide polymerization, the solvent filtered out carries out rectifying
After recycle.However the method has problems in that at 3 points：First, a large amount of solvents can be remained in filter cake, by after washing again into
Row rectifying recycling energy consumption is big；Second is that both also containing by-product salt containing solvent in the mother liquor that filter cake detaches after washing, three mixes
Conjunction is difficult to detach；Third, product particle is big and uneven, the catalyst and by-product of synthesis are still wrapped in polymer
Portion is difficult to purify, and causes product purity not high, limits the application range of resin.
Against the above deficiency, in the production process of polyphenylene sulfide, after a kind of Polymer Synthesizing to crystal type
The method that the efficient recycling method and product of solvent are easy to purifying, solves solvent in current polyphenylene sulfide commercial process
The problem of loss is big, and energy consumption is high.
Invention content
The technical problem to be solved by the present invention is to provide crystal type Polymer Synthesizing method for recovering solvents, this method can be realized molten
Agent high efficiente callback utilizes, and product automatically forms uniform powder so as to conducive to purifying washing.
Crystal type Polymer Synthesizing method for recovering solvents of the present invention, includes the following steps：
1) after the completion of solution polymerization, reaction solution is flashed in the state of stirring, negative pressure, heating, recycling design；
2) the powdered product washing after recycling design, drying are to get crystal type high molecular material.
Wherein, the stirring is stirred using ribbon screw, and by the way of lower stirring, and stir speed (S.S.) is 40~60r/
min；The negative pressure is less than 0.05MPa for pressure；The temperature of the heating is less than 30~40 DEG C of solvent boiling point temperature.
Further, the flash distillation is using flash vaporization kettle, and the flash vaporization kettle includes flash vaporization kettle tank body, in the flash vaporization kettle tank body
Flash vaporization kettle blender is provided with, the flash vaporization kettle tank body is additionally provided with flash vaporization kettle feed inlet, flash vaporization kettle discharge port and vacuum interface；
The vacuum interface is linked in sequence with condenser, vacuum pump；The flash vaporization kettle blender is helix(ribbon type) agitator, and is stirred under using
The mode of mixing is set；Flash vaporization kettle stirring motor, the flash vaporization kettle stirring motor output terminal and the sudden strain of a muscle are provided with outside flash vaporization kettle tank body
Steam the connection of kettle blender；Flash vaporization kettle tank wall is enclosed with electric heating cover.
Second technical problem that the present invention solves is to provide the production method of polyphenylene sulfide.
The production method of polyphenylene sulfide of the present invention, includes the following steps：
A, N-Methyl pyrrolidone, wateriness sodium sulfide, lithium chloride are mixed, is warming up to 200 DEG C of progress under nitrogen protection
Wateriness sodium sulfide dissolving dehydration, dewatering time are 2~2.5h；
B, after being dehydrated, paracide is added in, keeps 250~280 DEG C, 1~2MPa of pressure of reaction temperature, polycondensation reaction 2~4
Hour, reaction was completed；
C, after reaction, reaction solution is flashed in the state of stirring, negative pressure, heating, recycling design；
D, the powdered product washing after recycling design, drying are to get polyphenylene sulfide.
Wherein, in molar ratio, Dui bis- Lv Ben ︰ Liuization Na ︰ Lvization Li ︰ N-Methyl pyrrolidones=1 ︰, 1 ︰, 0.29~0.31 ︰ 7
~8.
Further, stirring is stirred using ribbon screw described in step c, and by the way of lower stirring, stir speed (S.S.)
For 40~60r/min；Heating temperature in step c is 160~170 DEG C, and negative pressure described in step c is less than 0.05MPa for pressure.
Further, deionized water is injected in the powdered product after step c recycling design to stir to form slurry, it is heated to wash
Rear separation of solid and liquid is washed, liquid recycles residual solvent using xylene extraction.
Preferably, the washing described in step d uses boiling water countercurrent washing；The drying is dry for 120~150 DEG C
It is dry.
Preferably, a, b step carry out in polymeric kettle, and the step c is in flash vaporization kettle described in claim 4
Middle progress；Wherein, the polymeric kettle includes polymeric kettle tank body, and agitation equipment of polymerization vessel and cold is provided in the polymeric kettle tank body
But coil pipe, the cooling coil are connected in the coolant circulation circuit outside polymeric kettle tank body, the polymeric kettle tank body
It is additionally provided with polymeric kettle feed inlet and polymeric kettle discharge port；The polymeric kettle discharge port is connect with flash vaporization kettle feed inlet；It is described poly-
Close kettle agitating device and include upper blender and for blender under screw, be provided with outside polymeric kettle tank body stirring motor mechanism and
Lower stirring motor mechanism, the upper stirring motor mechanism output terminal are connect with upper blender, the lower stirring motor mechanism output
End is connect with lower blender；Polymeric kettle tank wall is enclosed with electric heating cover.
Wherein, b step after reaction, by the pressure between pressure-equalizing pipe equilibrium polymerization kettle and flash vaporization kettle, then is incited somebody to action
Reaction solution is put into flash vaporization kettle.
The polyphenylene sulfide prepared by the method for the present invention is used as thermoplastic resin, 285~289 DEG C of the fusing point of product,
Weight average molecular weight is 45000~52000, and molecular weight dispersion coefficient is 1.1~1.2, and chloride ion content is less than 50ppm.Due to
Product grain size after flash distillation is small and uniform, is easy to wash, and solves sodium chloride content height and difficult removing in the product of conventional method
The problem of causing product quality low.
Compared with prior art, the invention has the advantages that：
The present invention overcomes solvent recovery high energy consumption in existing crystal type Polymer production technique, loss is big the problem of, together
When also overcome the inorganic salt particle cleaning that product particle in traditional handicraft wraps up and do not cause totally macromolecule product purity not high
The problem of, a kind of new method for recovering solvents is provided for the field of polymers, simplifies production procedure.This method so that material is molten
Solvent rapid evaporative condenser recycling under the action of high negative pressure and heating strong mixing in liquid, while material becomes powdery, favorably
In being further processed, this does not just destroy the macromolecule of polyphenylene sulfide while purifying products and solvent recovery is solved
Chain ensure that the purity and performance of product, reduce the energy consumption of recycling design.Particularly suitable for the industrial metaplasia of polyphenylene sulfide
Production.Using the polyphenylene sulfide purity prepared by preparation method of the present invention is high, performance is stablized, aerospace, electricity can be applied to
The fields such as son, machinery, medical treatment, chemical industry.
Description of the drawings
Fig. 1 is the structure diagram of polymeric kettle used in the present invention；
Fig. 2 is the structure diagram of flash vaporization kettle used in the present invention；
Reference numeral is in figure：Polymeric kettle 1, polymeric kettle tank body 11, upper blender 12, upper stirring motor mechanism 121, under stir
It mixes device 13, lower stirring motor mechanism 131, cooling coil 14, polymeric kettle feed inlet 15, polymeric kettle discharge port 16, flash vaporization kettle 2, dodge
Steam kettle tank body 21, flash vaporization kettle blender 22, flash vaporization kettle stirring motor 221, flash vaporization kettle feed inlet 25, flash vaporization kettle discharge port 26, true
Null interface 27.
Specific embodiment
Crystal type Polymer Synthesizing method for recovering solvents of the present invention, includes the following steps：
1) after the completion of solution polymerization, reaction solution is flashed in the state of stirring, negative pressure, heating, recycling design；
2) the powdered product washing after recycling design, drying are to get crystal type high molecular material.
In crystal type Polymer Synthesizing method for recovering solvents of the present invention, stirring is one of crucial influence factor, by stirring
It mixes and plays broken effect, the powder that can make precipitation is thinner, and preferred stir speed (S.S.) is 40~60r/min.To overcome in stirring
The big problem of resistance, the stirring are stirred using ribbon screw, and by the way of lower stirring.
Preferably, the negative pressure is less than 0.05MPa for pressure；The temperature of the heating is molten less than to be recycled
30~40 DEG C of agent boiling temperature.
Further, the flash distillation in the method for the present invention preferably uses flash vaporization kettle, and the structure of the flash vaporization kettle is as shown in Figure 1.
The flash vaporization kettle includes flash vaporization kettle tank body 21, and flash vaporization kettle blender 22, the flash vaporization kettle are provided in the flash vaporization kettle tank body 21
Tank body 21 is additionally provided with flash vaporization kettle feed inlet 25, flash vaporization kettle discharge port 26 and vacuum interface 27；It is vacuum interface 27 and condenser, true
Sky pump is linked in sequence；Flash vaporization kettle stirring motor 221 is provided with outside flash vaporization kettle tank body 21, the flash vaporization kettle stirring motor 221 exports
End is connect with the flash vaporization kettle blender 22；21 outer wall of flash vaporization kettle tank body is enclosed with electric heating cover.
During work, the reaction solution after the completion of solution polymerization is entered into flash vaporization kettle tank body 21 through flash vaporization kettle feed inlet 25
It is interior, vacuumize process is then carried out, while to the solution in flash vaporization kettle tank body 21 to flash vaporization kettle tank body 21 by vacuum interface 27
Heating and thermal insulation is carried out, and starting driving motor makes flash vaporization kettle blender 22 work.In this process, solution is in the flash distillation of high negative pressure
Heating flash evaporation and pass through in kettle tank body 21 and steam kettle blender 22 and stir, can rapidly extract evaporation of the solvent directly through vacuum interface 27 out
Row condensation recycling is tapped into, since solution boiling point reduces under negative pressure state, and the entire solvent recovery time is substantially shorter, in ribbon
Into uniform powdery, this does not just destroy poly- product while purifying products and solvent recovery is solved under the action of screw strong mixing
The macromolecular chain of object is closed, the purity and performance of product is ensure that, reduces energy consumption.
Multiple heating mode can be used in above-mentioned flash vaporization kettle, heating unit, such as burns using infrared heating or using coal, gas
It is heated Deng to the solution in flash vaporization kettle tank body 21.In order to more preferably improve mixing effect, band in product precipitation process is overcome
The powerful resistance come, the steaming kettle blender 22, which has, should be ribbon screw structure, and agitating mode should also take lower stirring side
Formula.
As preferred embodiments of the present invention, the condition of the flash distillation is related with the property of the solvent in reaction solution, polymerization
Flash vaporization kettle chuck afterwards keeps heating, and flash vaporization kettle jacket temperature is less than 30~40 DEG C of solvent boiling point temperature；Agitator speed is not low
In 50rpm；Flash vaporization kettle is evacuated to form negative pressure state through vacuum system, and pressure will be less than 0.05MPa in kettle.
Preferably, above-mentioned steps 2) injection deionized water stirs to form slurry in powdered product after recycling design
Expect, separation of solid and liquid after heated washing, due to containing residual solvent in liquid, be delivered in extractor and returned using xylene extraction
It receives, recycles.
Further, the solid after above-mentioned separation of solid and liquid uses boiling water countercurrent washing, according to circumstances washable multiple.
The method of the present invention is suitable for the industrialized production of polyphenylene sulfide.
The raw material of the industrialized production of the polyphenylene sulfide is：Paracide, wateriness sodium sulfide, catalyst chlorination
Lithium, N-Methyl pyrrolidone.The specific steps are：
A, by the production solvent N-methyl pyrilidone of polyphenylene sulfide, raw material wateriness sodium sulfide, catalyst lithium chloride
Mixing is warming up to 200 DEG C and carries out wateriness sodium sulfide dissolving dehydration under nitrogen protection, and dewatering time is 2~2.5h；
B, after being dehydrated, raw material paracide is added in, keeps 250~280 DEG C, 1~2MPa of pressure of reaction temperature, polycondensation reaction
2~4 hours, reaction was completed, and internal coil cooling, which can be used, in this stage ensures that interior temperature is stablized；
C, after reaction, reaction solution is flashed in the state of stirring, negative pressure, heating, recycling design；
D, the powdered product washing after recycling design, drying are to get polyphenylene sulfide.
Further, the mol ratio of the raw material is：Dui bis- Lv Ben ︰ Liuization Na ︰ Lvization Li ︰ N-Methyl pyrrolidones=
1 ︰, 1 ︰, 0.29~0.31 ︰ 7~8.
When step c is flashed, the stirring is stirred, and by the way of lower stirring, stir speed (S.S.) is using ribbon screw
40~60r/min；Heating temperature in step c is 160~170 DEG C, and negative pressure described in step c is less than 0.05MPa for pressure.
Preferably, deionized water is injected in the powdered product after step c recycling design to stir to form slurry, through adding
Hot wash washs rear separation of solid and liquid, and liquid recycles residual solvent using xylene extraction.
Injection deionized water stirs to form slurry in granular material after step c flash distillation recycling designs, after heated washing
Separation of solid and liquid due to containing a small amount of residual solvent in liquid, is delivered in extractor and is recycled using xylene extraction, cycle makes
With.
In the production method of polyphenylene sulfide of the present invention, the powdered product of Step d preferably uses boiling water countercurrent washing, more
It reduces water consumption.The drying of Step d is best with 120~150 DEG C of dryings of temperature.
Preferably, present invention preferably employs polymeric kettles and flash vaporization kettle to be reacted, wherein, a, b step are poly-
It closes and is carried out in kettle, step c carries out in flash vaporization kettle；The structure of flash vaporization kettle as described above, structure such as Fig. 1 institutes of polymeric kettle
Show.
Polymeric kettle includes polymeric kettle tank body 11, and agitation equipment of polymerization vessel and cooler pan are provided in the polymeric kettle tank body 11
Pipe 14, the cooling coil 14 are connected in the coolant circulation circuit outside polymeric kettle tank body 11, the polymeric kettle tank
Body 11 is additionally provided with polymeric kettle feed inlet 15 and polymeric kettle discharge port 16；The polymeric kettle discharge port 16 and flash vaporization kettle feed inlet 25
Connection；The agitation equipment of polymerization vessel includes upper blender 12 and is blender 13 under screw, is set outside polymeric kettle tank body 11
You Shang stirring motors mechanism 121 and lower stirring motor mechanism 131, upper 121 output terminal of stirring motor mechanism and upper blender
12 connections, lower 131 output terminal of stirring motor mechanism are connect with lower blender 13；11 outer wall of polymeric kettle tank body is enclosed with electricity and adds
Hot jacket.
When in reaction raw materials input polymeric kettle tank body 11, upper blender 12 is mainly stirred liquid charging stock, lower stirring
Device 13 mainly acts on solid material of the product in tank body bottom.It is further preferred that the lower blender 13 can be screw rod
Formula blender.Cooling coil 14 is used to that the raw material in tank body to be maintained to be in preference temperature, when synthesizing due to polyphenylene sulfide, meeting
Exothermic reaction occurs, tank body temperature is excessively high in order to prevent, can be passed through cooling agent into cooling coil 14 to realize cooling.It is cold
But coil pipe 14 can be preferably the coiled coil multilayer as spring in polymeric kettle tank body 11, to increase cooling coil 14
With the contact area of raw material, cooling efficiency is improved, while but also each position can uniform decrease in temperature in tank body.Cooling coil 14
Interior can be passed through cold water or other to cool down the substance of heat absorption.Cooling coil 14 is connected to outside polymeric kettle tank body 11
In the coolant circulation circuit in portion, such as can be that cooling coil 14 is connected in the chilled(cooling) water return (CWR) with circulating pump, cycle
Pump driving flow circulates in cooling coil 14, takes away the waste heat in polymeric kettle tank body 11.Polymeric kettle completes polymerization
Reaction solution after reaction enters from polymeric kettle discharge port 16 in flash vaporization kettle tank body 21, is flashed.
Further, b step in polymeric kettle after reaction, pass through pressure-equalizing pipe equilibrium polymerization kettle and flash vaporization kettle
Between pressure, then reaction solution is put into flash vaporization kettle.
The polyphenylene sulfide prepared by the method for the present invention is used as thermoplastic resin, 285~289 DEG C of the fusing point of product,
Weight average molecular weight is 45000~52000, and molecular weight dispersion coefficient is 1.1~1.2, and chloride ion content is less than 50ppm.Due to
Product grain size after flash distillation is small and uniform, is easy to wash, and solves sodium chloride content height and difficult removing in the product of conventional method
The problem of causing product quality low.
The specific embodiment of the present invention is further described with reference to embodiment, is not therefore limited the present invention
System is among the embodiment described range.
Embodiment 1
Mol ratio according to raw material is the more water Liuization Na ︰ Lvization Li ︰ N-Methyl pyrrolidones of Dui bis- Lv Ben ︰=1 ︰, 1 ︰
0.3 ︰ 7 gets out raw material.By the production solvent N-methyl pyrilidone of polyphenylene sulfide, raw material wateriness sodium sulfide, catalysis
Agent lithium chloride is put into polymeric kettle successively, and it is small to be warming up to 200 DEG C of progress wateriness sodium sulfide dissolving dehydrations 2 under nitrogen protection
When, raw material paracide is added in after being then cooled to 165 DEG C, is warming up to 260 DEG C of polymerization temperature, keeps pressure 1.1MPa in kettle left
The right side avoids high temperature from fluctuating by cooling coil, and the pressure that polymerisation is opened after 3 hours between polymeric kettle and flash vaporization kettle is put down
Material, is all put into flash vaporization kettle by weighing apparatus pipe after pressure balance, opens stirring and vacuum system, and it is 160 to keep flash vaporization kettle temperature
DEG C or so, pressure is less than 0.05MPa, stir speed (S.S.) 50r/min in kettle, stops when solvent flux is greatly reduced in device to be condensed
Only vacuum closes heating, and deionized water is injected into flash vaporization kettle and stirs to form slurry, slurry is centrifuged, the liquid after separation
The xylene extraction that body is delivered in extractor recycles residual solvent, boiling water countercurrent washing 5 times in Solid Conveying and Melting to washing kettle, then
In 150 DEG C of dry polyphenylene sulfides for obtaining the present invention.Its performance is shown in Table 1.
1 polyphenylene sulfide performance of table
| Characteristic | Test method | Unit | Polyphenylene sulfide prepared by embodiment 1 |
| Weight average molecular weight | Exclusion chromatography | *104 | 4.8 |
| The coefficient of dispersion | Exclusion chromatography | - | 1.11 |
| Chloride ion content | Atomic absorption method | ppm | 32 |
| Glass transition temperature | DSC | ℃ | 88 |
| Fusing point | DSC | ℃ | 290 |
| Limited oxygen index | ISO 4589 | %O2 | 44 |
| Tensile strength | GB/T1040.2 | Mpa | 81 |
Continued 1
Embodiment 2
Mol ratio according to raw material is the more water Liuization Na ︰ Lvization Li ︰ N-Methyl pyrrolidones of Dui bis- Lv Ben ︰=1 ︰, 1 ︰
0.3 ︰ 8 gets out raw material.By the production solvent N-methyl pyrilidone of polyphenylene sulfide, raw material wateriness sodium sulfide, catalysis
Agent lithium chloride is put into polymeric kettle successively, and it is small to be warming up to 200 DEG C of progress wateriness sodium sulfide dissolving dehydrations 2.5 under nitrogen protection
When, raw material paracide is added in after being then cooled to 165 DEG C, is warming up to 270 DEG C of polymerization temperature, keeps pressure 1.1MPa in kettle left
The right side avoids high temperature from fluctuating by cooling coil, and the pressure that polymerisation is opened after 4 hours between polymeric kettle and flash vaporization kettle is put down
Material, is all put into flash vaporization kettle by weighing apparatus pipe after pressure balance, opens stirring and vacuum system, and it is 160 to keep flash vaporization kettle temperature
DEG C or so, pressure is less than 0.05MPa, stir speed (S.S.) 40r/min in kettle, stops when solvent flux is greatly reduced in device to be condensed
Only vacuum closes heating, and deionized water is injected into flash vaporization kettle and stirs to form slurry, slurry is centrifuged, the liquid after separation
The xylene extraction that body is delivered in extractor recycles residual solvent, boiling water countercurrent washing 5 times in Solid Conveying and Melting to washing kettle, then
In 150 DEG C of dry polyphenylene sulfides for obtaining the present invention.Its performance is shown in Table 2.
2 polyphenylene sulfide performance of table
In conclusion using " synthesis-flash distillation crushes-solvent recovery-boiling water adverse current and washes during above-mentioned specific embodiment
Wash-be dried in vacuo-be modified granulation " set technique route effectively solve the problems, such as product difficulty purifying, solvent difficulty recycling,
So that product purity is high, performance is stablized.Being used simultaneously by solvent recovery cycle not only reduces production cost, but also solve environmental protection
Pollution problem.
Claims (5)
1. the production method of polyphenylene sulfide, which is characterized in that its step are as follows：
A, N-Methyl pyrrolidone, wateriness sodium sulfide and lithium chloride are mixed, is warming up to 200 DEG C under nitrogen protection and carries out more water
Vulcanized sodium dissolving dehydration, dewatering time are 2~2.5 hours；
B, after being dehydrated, paracide is added in, keeps 250~280 DEG C, 1~2MPa of pressure of reaction temperature, polycondensation reaction 2~4 is small
When, reaction was completed；
C, after reaction, reaction solution is flashed in the state of stirring, negative pressure, heating, recycling design；
D, the powdered product washing after recycling design, drying are to get polyphenylene sulfide；
Stirring is stirred using ribbon screw described in step c, and by the way of lower stirring, and stir speed (S.S.) is 40~60r/min；
Heating temperature in step c is 160~170 DEG C, and negative pressure described in step c is less than 0.05MPa for pressure；
The a, b step carry out in polymeric kettle, and step c carries out in flash vaporization kettle；Wherein, the polymeric kettle includes polymeric kettle tank
Body (11), the polymeric kettle tank body (11) is interior to be provided with agitation equipment of polymerization vessel and cooling coil (14), the cooling coil
(14) it is connected in the external coolant circulation circuit of polymeric kettle tank body (11), the polymeric kettle tank body (11) is additionally provided with
Polymeric kettle feed inlet (15) and polymeric kettle discharge port (16)；The polymeric kettle discharge port (16) connects with flash vaporization kettle feed inlet (25)
It connects；The agitation equipment of polymerization vessel includes upper blender (12) and is blender (13) under screw, and polymeric kettle tank body (11) is outside
It is provided with stirring motor mechanism (121) and lower stirring motor mechanism (131), upper stirring motor mechanism (121) output terminal
It is connect with upper blender (12), lower stirring motor mechanism (131) output terminal is connect with lower blender (13)；Polymeric kettle tank body
(11) outer wall is enclosed with electric heating cover；
The flash vaporization kettle includes flash vaporization kettle tank body (21), and flash vaporization kettle blender (22) is provided in the flash vaporization kettle tank body (21),
The flash vaporization kettle tank body (21) is additionally provided with flash vaporization kettle feed inlet (25), flash vaporization kettle discharge port (26) and vacuum interface (27)；Institute
Vacuum interface (27) is stated to be linked in sequence with condenser, vacuum pump；The flash vaporization kettle blender (22) is helix(ribbon type) agitator, and is adopted
It is set with lower agitating mode；Flash vaporization kettle stirring motor (221), the flash vaporization kettle stirring motor are provided with outside flash vaporization kettle tank body (21)
(221) output terminal is connect with the flash vaporization kettle blender (22)；Flash vaporization kettle tank body (21) outer wall is enclosed with electric heating cover；
And b step is after reaction, is put by the pressure between pressure-equalizing pipe equilibrium polymerization kettle and flash vaporization kettle, then by reaction solution
Enter in flash vaporization kettle.
2. the production method of polyphenylene sulfide according to claim 1, it is characterised in that：In molar ratio, Dui bis- Lv Ben ︰ vulcanize
Na ︰ Lvization Li ︰ N-Methyl pyrrolidones=1 ︰, 1 ︰, 0.29~0.31 ︰ 7~8.
3. the production method of polyphenylene sulfide according to claim 1 or 2, it is characterised in that：Powder after step c recycling design
It injects deionized water in shape product to stir to form slurry, separation of solid and liquid after heated washing, liquid is recycled using xylene extraction
Residual solvent.
4. the production method of polyphenylene sulfide according to claim 1 or 2, it is characterised in that：Washing described in step d is adopted
With boiling water countercurrent washing；The drying is 120~150 DEG C of dryings.
5. the production method of polyphenylene sulfide according to claim 3, it is characterised in that：Washing described in step d uses
Boiling water countercurrent washing；The drying is 120~150 DEG C of dryings.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101717510A (en) * | 2009-10-28 | 2010-06-02 | 宋祥会 | Process for producing polyphenyl thioether |
| CN102317353A (en) * | 2009-02-13 | 2012-01-11 | 切弗朗菲利浦化学公司 | System and method for reducing off-gassing of polyphenylene sulfide |
| CN202777864U (en) * | 2012-08-28 | 2013-03-13 | 成都中海数据处理服务有限公司 | Energy-saving distillation device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102317353A (en) * | 2009-02-13 | 2012-01-11 | 切弗朗菲利浦化学公司 | System and method for reducing off-gassing of polyphenylene sulfide |
| CN101717510A (en) * | 2009-10-28 | 2010-06-02 | 宋祥会 | Process for producing polyphenyl thioether |
| CN202777864U (en) * | 2012-08-28 | 2013-03-13 | 成都中海数据处理服务有限公司 | Energy-saving distillation device |
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