CN109929110A - The method of polyphenylene sulfide is recycled from synthesis polyphenylene sulfide slurry - Google Patents
The method of polyphenylene sulfide is recycled from synthesis polyphenylene sulfide slurry Download PDFInfo
- Publication number
- CN109929110A CN109929110A CN201711364077.7A CN201711364077A CN109929110A CN 109929110 A CN109929110 A CN 109929110A CN 201711364077 A CN201711364077 A CN 201711364077A CN 109929110 A CN109929110 A CN 109929110A
- Authority
- CN
- China
- Prior art keywords
- polyphenylene sulfide
- slurry
- synthesis
- screening
- sieve
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a kind of methods that polyphenylene sulfide is separated and recovered from synthesis polyphenylene sulfide slurry, it includes preliminary sieves with continuous screen in two steps, in order to make side product chlorinated sodium and the particle of polyphenylene sulfide oligomer of polyphenylene sulfide and generation have biggish difference, phase separation agent can also be added in polyphenylene sulfide synthesis process, this method is very simple, it is low for equipment requirements, byproduct sodium chloride after processing in PPS resin, auxiliary agent, polyphenylene sulfide oligomer content is low, substantially increase the quality of PPS resin, compared with prior art, overall cost is lower.
Description
Technical field
The present invention relates to a kind of methods for recycling polyphenylene sulfide, and more precisely, the present invention relates to one kind from synthesis
Low poly- of impurity content can be made by this method in the method that polyphenylene sulfide is separated and recovered in polyphenylene sulfide slurry
Diphenyl sulfide naval stores.
Background technique
Poly (arylene sulfide), for example, polyphenylene sulfide, poly- 2,4- 3,5-dimethylphenyl sulfide, poly- 4,4- biphenylene vulcanization
Object, especially polyphenylene sulfide are a kind of special engineering plastics that mechanical performance is excellent, have excellent heat resistance, electrical property and
Rigidity, is widely used in a variety of materials field, such as automobile, electric part.
Currently, the method for production polyphenylene sulfide is usually to be existed using dihalo- substituted aromatic compound and alkali metal sulphide
Condensation polymerization reaction is carried out in polar organic solvent, such as under high temperature and pressure using p- dichloro-benzenes and vulcanized sodium in N- methyl -2-
It polymerize in pyrrolidinone solvent, the slurry containing polyphenylene sulfide is made, filtering slurry recycles to obtain polyphenylene sulfide.
However, in the production technology of above-mentioned polyphenylene sulfide, p- dichloro-benzenes and vulcanized sodium polymerization reaction, in addition to generating
Outside polyphenylene sulfide, side product chlorinated sodium is also generated, the sodium chloride of generation does not dissolve in n-methyl-2-pyrrolidone solvent,
Meanwhile in polymerization process, a small amount of polyphenylene sulfide oligomer, that is, the substance of low molecular weight can be also generated, it is such as poly-
Diphenyl sulfide tripolymer, polyphenylene sulfide tetramer etc..
In slurry made from above-mentioned technique, main component is polyphenylene sulfide (PPS) resin of high molecular weight, by-product chlorination
Sodium, the solvent and auxiliary agent of synthesis, a small amount of polyphenylene sulfide oligomer, each component mass percentage and particle diameter distribution are as follows:
The method of impurity is that purifying polyphenylene sulfide is washed with water in conventional reduction polyphenylene sulfide slurry.By polyphenyl
When thioether slurry filtration recycles polyphenylene sulfide, sodium chloride and polyphenylene sulfide oligomer are combined together with polyphenylene sulfide,
A large amount of water is needed when washing Purification Resin, generates the largely wash water containing n-methyl-2-pyrrolidone solvent and sodium chloride, this
Part wash water, which needs to handle, to be discharged, or recycling solvent therein, this needs extraly equipment and operating cost.In addition,
Polyphenylene sulfide oligomer is not dissolved in solvent and water, and when washing Purification Resin, polyphenylene sulfide oligomer and organic solvent can be protected
It stays in resin, reduces naval stores quality.
In this case, Japanese patent application discloses No.207027/1995 (Heisei7) and discloses a kind of method,
In the case where being polymerization solvent using n-methyl-2-pyrrolidone, vulcanized sodium is replaced to carry out polymerization reaction using lithium sulfide,
Since the lithium chloride of generation dissolves in certain amount solvent, it, would not when slurry filtration is recycled polyphenylene sulfide
There is by-product to stay in polyphenylene sulfide, so that alkali halide is not contained in the wash water of washing polyphenylene sulfide,
Solvent therein is recycled to be easy for mostly.
Chinese patent application CN1624023A discloses a kind of purifying refining methd of macromolecular weight poly benzene thioether resin, it
It is that the powder of polyphenylene sulfide or pellet are directly subjected to vacuum high-temperature destructive distillation, utilizes organic impurities and macromolecule polyphenylene sulfide
The boiling point of ether resin is different, and organic impurities are evaporated and overflows and separates with macromolecule polyphenylene sulfide, to reach purification
Purpose.But this method needs a set of more complicated equipment and technique to handle, the energy of consuming is more, the cost of processing
It is very high.
In conclusion a kind of at low cost, simple process how is found in routinely production polyphenylene sulfide, can be effective
The method for removing by-product in polyphenylene sulfide becomes current technical problem urgently to be resolved.
Summary of the invention
The shortcomings that it is an object of the invention to overcome the above-mentioned prior art and provide a kind of from synthesis polyphenylene sulfide material
In slurry separate and recover polyphenylene sulfide method, by this method can be made sodium chloride, polyphenylene sulfide oligomer etc. it is miscellaneous
The low polyphenylene sulfide of matter content.
In order to complete above-mentioned purpose, researcher of the invention is had conducted intensive studies, as a result, it has been found that, it is of the invention
Purpose can be completed in the following way, i.e., polyphenylene sulfide synthesis slurry is separated off solid by-product by screening process
Sodium chloride and polyphenylene sulfide oligomer impurity.
Further, the present invention includes the following steps:
(1) preliminary screening: synthesis polyphenylene sulfide slurry is uniformly mixed, the sieve of 60-200 mesh is then passed through
Filtering, obtains on-the-sieve material and undersize material, wherein undersize material obtains filtrate and filter cake after passing through separating and filtering again；
(2) continuous screening: again by -200 mesh screen mistake of 60 mesh after above-mentioned filtrate and above-mentioned on-the-sieve material are mixed with beating
Filter, undersize material obtain new filtrate and new filter cake after passing through separating and filtering, are so repeated several times, obtained on-the-sieve material is i.e.
For polyphenylene sulfide.
It should be noted that can be used as the oligomer in the solvent soluble resin of the solvent mixed with on-the-sieve material,
And insoluble or oligodynamical high molecular weight PPS and salt, it includes: n-methyl-2-pyrrolidone solvent, acetone, ethyl alcohol etc.,
But in specific production process, use filtered filtrate as this solvent be most economical.
It is an option that in the present invention, control on-the-sieve material thickness does not surpass during preliminary screening and continuous screening
Cross 10mm.
The present invention is to use the method for screening by the side product chlorinated sodium and polyphenylene sulfide oligomer in polyphenylene sulfide slurry
It is separated off from polyphenylene sulfide, therefore, it is necessary to the side product chlorinated sodium of the polyphenylene sulfide of preparation and generation and poly-
The particle of diphenyl sulfide oligomer has biggish difference.In the polymerization reaction of production polyphenylene sulfide, side product chlorinated sodium and polyphenyl
The particle of thioether oligomer object is very tiny, specifically, the particle of side product chlorinated sodium and polyphenylene sulfide oligomer 200 mesh with
Under, therefore, as long as the control of the particle size of polyphenylene sulfide is being greater than side product chlorinated sodium and polyphenylene sulfide oligomer
Particle just, preferably by polyphenylene sulfide Grain size controlling more than 100 mesh, or by the polyphenylene sulfide of 99wt%
Grain control is more than 100 mesh.
By the control of polyphenylene sulfide grain graininess more than 100 mesh, be worth selection is that can close in polyphenylene sulfide
At phase separation agent is added in the process, after polymerization reaction, phase separation agent can be such that the generation of polyphenylene sulfide slurry mutually separates, and be divided into
Solvent phase containing solvent and the resin phase containing resin and solvent.Cooling, the tree obtained by this slurry for occurring mutually to separate
Rouge particle has biggish grain graininess, can satisfy the needs that the present invention sieves.The reality for the phase separation agent that the suitable present invention uses
Example include the mixture of water, lithium chloride and the two, it is preferable to use lithium chloride and water mixture, be added and mutually separate in the present invention
The weight of agent is the 0.5%-3% for synthesizing slurry total weight.Wherein, water and lithium chloride can mix in any proportion, preferably
Hybrid plan is water: lithium chloride=95: 5.
In polyphenylene sulfide synthesis process be added phase separation agent after, in polyphenylene sulfide slurry each component mass percentage and
Particle diameter distribution is as follows:
As it can be seen that be added phase separation agent after be added phase separation agent before PPS resin and byproduct sodium chloride, auxiliary agent, polyphenylene sulfide
The particle size range of ether oligomer has bigger difference, more conducively sieves.
Method of the present invention, mechanism are to utilize PPS resin and byproduct sodium chloride, auxiliary agent, polyphenylene sulfide oligomer
Partial size it is different and carry out initial gross separation, then by the organic substance in filtrate dissolution on-the-sieve material, repeatedly for several times
By in polyphenylene sulfide side product chlorinated sodium and polyphenylene sulfide oligomer be reduced to suitable level；In synthesis PPS resin
Phase separation agent is added in the process, so that the partial size difference of PPS resin and above-mentioned impurity is bigger, the more conducively separation in later period.It is this
Method is very simple, low for equipment requirements, byproduct sodium chloride, auxiliary agent, polyphenylene sulfide oligomer content after processing in PPS resin
It is low, the quality of PPS resin is substantially increased, compared with prior art, overall cost is lower.
Specific embodiment
Below by embodiment, the present invention is further illustrated, but the present invention is not only limited in these examples.
Comparative example: the preparation of polyphenylene sulfide.
N-methyl-2-pyrrolidone 30kg is added in the one 60 liters stainless steel autoclaves with magnetic stirring apparatus,
Industrial sodium sulfide (Na2S content 60.01wt%), sodium acetate 1.2kg, sodium hydroxide 300g are stirred under nitrogen protection, and will
Reaction kettle is gradually warmed up to 204 DEG C, distills out liquid 9.6kg, wherein water content 19.32wt%.Then by material in reactor
170 DEG C are cooled to hereinafter, o-dichlorobenzene 8.05kg is added.Continue to be passed through nitrogen, closed reactor, until reacting kettle inner pressure
Reach 0.1MPa (gauge pressure), stopping is passed through nitrogen.Material in reactor is increased to 230 DEG C, keeps the thermotonus 1 hour,
Then temperature is increased to 260 DEG C, the reaction was continued at such a temperature 3 hours.After the reaction was completed, material in reactor is cooled to
Room temperature.It by gained slurry filtration, is washed, is filtered with a large amount of deionized waters, it is 6 hours dry at 105 DEG C, obtain polyphenylene sulfide resin
Rouge 5.6kg, yield 96.3% (in terms of vulcanized sodium) contain solid sodium chloride 5.8kg in slurry.
Wherein, in slurry made from above-mentioned technique, main component is polyphenylene sulfide (PPS) resin of high molecular weight, secondary
Sodium chloride is produced, the solvent and auxiliary agent of synthesis, a small amount of polyphenylene sulfide oligomer, each component mass percentage and particle diameter distribution are such as
Following table:
It obtains in polyphenylene sulfide finished product, contains byproduct sodium chloride, the solvent and auxiliary agent of synthesis, a small amount of polyphenylene sulfide
The amount of oligomer is respectively as follows: 0.3%, 0.1%, 0.15% and 3.1%
Embodiment 1:
Due to the polyphenylene sulfide and byproduct sodium chloride of synthesis and the solvent and auxiliary agent of synthesis, a small amount of polyphenylene sulfide is neat
Polymers partial size has apparent difference, and slurry can be such that resin separates with by-product salt and oligomer by sieving machine.Firstly, preliminary
Screening: synthesis polyphenylene sulfide slurry is uniformly mixed, then by the screen to filtrates of 60 mesh, obtain on-the-sieve material and
Undersize material, wherein undersize material obtains filtrate and filter cake after passing through separating and filtering again；
On-the-sieve material after screening, main ingredient are as follows.
Table: on-the-sieve material component and content after 1 primary dcreening operation
By-products content is substantially reduced after screening as can be seen from the above table.However for PPS, after primary dcreening operation
Salt content or relatively high in on-the-sieve material, this is because fine grain salt is wrapped in resin in screening process, herein
Salt therein cannot be reduced in secondary screening process again.Therefore screening must be carried out again more preferably to reach of the invention
Purpose.
Undersize material after primary dcreening operation, obtains the solid material for being rich in salt after centrifuge separation and salt concentration is few
Filtrate.This filtrate and the on-the-sieve material after primary dcreening operation are carried out being mixed to get secondary slurry, obtained secondary slurry
Screening process identical with last time is carried out, the on-the-sieve material of regrading is obtained.Its component is as follows:
Table 2: the on-the-sieve material component and content of regrading
From the point of view of upper table, obtained on-the-sieve material can also be sieved again according to the above method, until salt content drops to
Satisfied degree.
Table 3: the on-the-sieve material component and content sieved three times
In screening process, the thickness of material not Ying Taihou.If material accumulation is too thick on compass screen surface in screening process, can hinder
Hinder the particle of side product chlorinated sodium and polyphenylene sulfide oligomer by sieve, to be retained in PPS resin, therefore preferably controls
On-the-sieve material thickness is no more than 10mm.Any type of sieving machine can be used in screening process, as long as by-product can be separated off
The particle of object sodium chloride and polyphenylene sulfide oligomer.It is preferable to use the sieving machines for having vibration device, make material will not
It is accumulated in screening process blocked up.
Polyphenylene sulfide after above-mentioned screening is repeatedly washed, PPS resin product is dried to obtain.PPS resin at
Containing byproduct sodium chloride in product, the amount of the solvent and auxiliary agent of synthesis, a small amount of polyphenylene sulfide oligomer is respectively as follows: 0.15%,
0.06%, 0.05% and 0.93%.
Embodiment 2:
In the polyphenylene sulfide synthesis process of comparative example, the lithium chloride that 5kg (account for slurry gross weight 0.5%) is added is made
It for phase separation agent, is separated using the method in such as embodiment 1, using the sieve of 100 mesh, first, second and third screening when screening
The on-the-sieve material component and content table of screening afterwards are as follows:
Table: on-the-sieve material component and content after 1 primary dcreening operation
Table 2: the on-the-sieve material component and content of regrading
Table 3: the on-the-sieve material component and content sieved three times
Polyphenylene sulfide after above-mentioned screening is repeatedly washed, PPS resin product is dried to obtain.PPS resin at
Containing byproduct sodium chloride in product, the amount of the solvent and auxiliary agent of synthesis, a small amount of polyphenylene sulfide oligomer is respectively as follows: 0.09%,
0.06%, 0.03%, 0.75%.
Embodiment 3:
In the polyphenylene sulfide synthesis process of comparative example, the water of 30kg (account for slurry gross weight 3%) is added as phase
Release agent is separated using the method in such as embodiment 1, using the sieve of 80 mesh when screening, after first, second and third screening
The on-the-sieve material component and content table of screening are as follows:
Table: on-the-sieve material component and content after 1 primary dcreening operation
Table 2: the on-the-sieve material component and content of regrading
Table 3: the on-the-sieve material component and content sieved three times
Polyphenylene sulfide after above-mentioned screening is repeatedly washed, PPS resin product is dried to obtain.PPS resin at
Containing byproduct sodium chloride in product, the amount of the solvent and auxiliary agent of synthesis, a small amount of polyphenylene sulfide oligomer is respectively as follows: 0.10%,
0.06%, 0.05%, 0.79%.
Embodiment 4:
In the polyphenylene sulfide synthesis process of comparative example, water and the chlorination of 30kg (account for slurry gross weight 3%) is added
Lithium mixture is as phase separation agent, wherein water: lithium chloride=95: 5, it is separated using the method in such as embodiment 1, when screening
Using the sieve of 70 mesh, the on-the-sieve material component and content table of the screening after first, second and third screening are as follows:
Table: on-the-sieve material component and content after 1 primary dcreening operation
Table 2: the on-the-sieve material component and content of regrading
Table 3: the on-the-sieve material component and content sieved three times
Polyphenylene sulfide after above-mentioned screening is repeatedly washed, PPS resin product is dried to obtain.PPS resin at
Containing byproduct sodium chloride in product, the amount of the solvent and auxiliary agent of synthesis, a small amount of polyphenylene sulfide oligomer is respectively as follows: 0.06%,
0.06%, 0.02%, 0.60%.
Claims (3)
1. a kind of method for recycling polyphenylene sulfide from synthesis polyphenylene sulfide slurry, it is characterised in that including walking as follows
It is rapid:
(1) preliminary screening: synthesis polyphenylene sulfide slurry is uniformly mixed, the sieve mistake of 60-200 mesh is then passed through
Filter, obtains on-the-sieve material and undersize material, wherein undersize material obtains filtrate and filter cake after passing through separating and filtering again；
(2) continuous screening: pass through -200 mesh net filtration of 60 mesh, sieve after above-mentioned filtrate and above-mentioned on-the-sieve material are mixed with beating again
Lower material obtains new filtrate and new filter cake after passing through separating and filtering, is so repeated several times, and obtained on-the-sieve material is poly-
Diphenyl sulfide resin.
2. the method according to claim 1 for recycling polyphenylene sulfide from synthesis polyphenylene sulfide slurry, special
Sign is that control on-the-sieve material thickness is no more than 10mm during preliminary screening and continuous screening.
3. the method according to claim 1 for recycling polyphenylene sulfide from synthesis polyphenylene sulfide slurry, special
Sign is to be also added into phase separation agent in the synthetic reaction process for being conventionally synthesized polyphenylene sulfide slurry.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711364077.7A CN109929110A (en) | 2017-12-18 | 2017-12-18 | The method of polyphenylene sulfide is recycled from synthesis polyphenylene sulfide slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711364077.7A CN109929110A (en) | 2017-12-18 | 2017-12-18 | The method of polyphenylene sulfide is recycled from synthesis polyphenylene sulfide slurry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109929110A true CN109929110A (en) | 2019-06-25 |
Family
ID=66982410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711364077.7A Pending CN109929110A (en) | 2017-12-18 | 2017-12-18 | The method of polyphenylene sulfide is recycled from synthesis polyphenylene sulfide slurry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109929110A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746302A (en) * | 2022-11-28 | 2023-03-07 | 宜宾学院 | Recovery process of materials in polyphenylene sulfide production process |
-
2017
- 2017-12-18 CN CN201711364077.7A patent/CN109929110A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115746302A (en) * | 2022-11-28 | 2023-03-07 | 宜宾学院 | Recovery process of materials in polyphenylene sulfide production process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0202537B1 (en) | Process for treating a polymer slurry | |
| KR102131164B1 (en) | Method for preparing of polyphenylene sulfide and low chlorine polyphenylene sulfide | |
| CN1326911C (en) | Process for producing and method of cleaning polyarylene sulfide, and method of purifying organic solvent used for cleaning | |
| CN109705347B (en) | Process method for separating oligomer from polyphenylene sulfide resin synthetic slurry | |
| US10731005B2 (en) | Method for producing granular polyarylene sulfide, method for increasing average particle size of granular polyarylene sulfide, method for enhancing particle strength of granular polyarylene sulfide, and granular polyarylene sulfide | |
| KR101927674B1 (en) | Process for producing polyarylene sulfide | |
| KR101928254B1 (en) | Process for producing polyarylene sulfide | |
| US20170158820A1 (en) | Polyarylene sulfide production method and polyarylene sulfide produced using production method | |
| CN1896119B (en) | Method for recovering polyphenyl resin from synthetic polyphenyl resin slurry | |
| CN109929110A (en) | The method of polyphenylene sulfide is recycled from synthesis polyphenylene sulfide slurry | |
| CN106278969A (en) | A kind of method of green syt 1 isothiocyanic acid base 2 chlorine 2 propylene | |
| CN106946757A (en) | A kind of method that the pyrrolidones of N methyl 2 is reclaimed from salt solution | |
| KR102141348B1 (en) | Method for producing granular polyarylene sulfide and granular polyarylene sulfide | |
| TWI795604B (en) | Separation and purification method of polyarylene sulfide and preparation method of polyarylene sulfide | |
| CN106084224A (en) | A kind of high whiteness poly arylidene thio-ester of narrow particle size distribution and preparation method thereof | |
| CN104877167B (en) | The method that adjuvant used lithium chloride recycles in polyphenylene sulfide resin production process | |
| EP0271253A2 (en) | Process for recovering a polyarylene sulfide | |
| CN108892687A (en) | A method of it preparing hexamethylphosphoramide while obtaining dimethylamine hydrochloride | |
| CN110105573B (en) | Method for reducing COD (chemical oxygen demand) of polyphenylene sulfide byproduct salt | |
| US11597800B2 (en) | Separation and recovery method of polyarlene sulfide | |
| JPS5989327A (en) | Recovery of granular polyarylene sulfide by use of evaporation | |
| EP3766867B1 (en) | Method for recovering amide-based compound | |
| CN104744238A (en) | Method for recovering glycolic acid in phenoxyacetic acid pesticide waste water | |
| US3993700A (en) | Purification of p-phenylphenol | |
| JP3446969B2 (en) | Method for producing lithium N-methylaminobutyrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190625 |