CN104072772A - Treatment method for polyphenylene sulfide resin slurry - Google Patents
Treatment method for polyphenylene sulfide resin slurry Download PDFInfo
- Publication number
- CN104072772A CN104072772A CN201410328177.4A CN201410328177A CN104072772A CN 104072772 A CN104072772 A CN 104072772A CN 201410328177 A CN201410328177 A CN 201410328177A CN 104072772 A CN104072772 A CN 104072772A
- Authority
- CN
- China
- Prior art keywords
- solid substance
- polyphenylene sulfide
- solvent
- solid
- washing
- 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 treatment method for polyphenylene sulfide resin slurry. After carrying out solid-liquid separation onto reactant slurry which completes polymerization reaction with participation of lithium chloride in NMP (non-methane products), a solvent left in solid is further removed at 180-240 DEG C to obtain solid containing a polyphenylene sulfide resin product; the treatment method is respectively carried out and completed through the following steps: (A), dispersing and washing in an organic amide and /or lactam solvent with pH value of 6-7.5 at 80-200 DEG C; and (B), dispersing and washing in a low-boiling point organic solvent mixed with NMP; and (C), dispersing and washing in aqueous liquor. After each operation is completed, the purified polyphenylene sulfide resin product is obtained. The method disclosed by the invention can realize continuous treatment on slurry, effectively lowers contents of oligomer, alkali metal salts and other impurities contained in the polyphenylene sulfide resin, improves color and luster of the product, greatly lowers usage amount of the solvent, lowers cost, improves production efficiency and effectively avoids a problem that performance of the product is affected as the product contacts with the environment.
Description
Technical field
This relates to a kind of poly-p-phenylene sulfide ether resin slurry, particularly to completing the treatment process of the reactant slurry after polyreaction under participating at N-Methyl pyrrolidone reaction medium catalyst neutralisation lithium chloride.
Background technology
Polyphenylene sulfide (PPS, full name is polyphenylene sulfide), it is a kind of special engineering plastics of excellent performance, again a kind of crystalline thermoplastic resin simultaneously, can be widely used in the numerous areas such as electronics, automobile, oil and chemical industry, textile manufacturing machine, military project and sophisticated technology, be a kind of indispensable chemical materials.The suitability for industrialized production of PPS mainly be take sodium sulphite and santochlor at present as raw material, under N-Methyl pyrrolidone (NMP) reaction medium solvent and lithium chloride catalysis, through dehydration polycondensation, forms.In the PPS product preparing through this process, can contain a large amount of Na
+, Cl
-deng mineral ion and oligopolymer composition.Mineral ion wherein can reduce the electrical insulation capability of PPS, and meeting etching electronic element; The existence of oligopolymer can destroy the mechanical property of material, causes adding producing the problems such as bubble man-hour.
For this reason, to completing the treatment process of the PPS slurry after polyreaction, roughly there are two kinds at present.A kind of is to report as European patent number EP0363995A2, and by after reaction paste flash distillation, then water or hydrocarbon compound be the remaining mixture reslurry in still, and then filtering separation, collects PPS resin.Another kind method, as US 4415729A report, the direct dilute with water of reactant slurry by completing after polyreaction, promotes to be separated, and then filters, and filter cake obtains PPS after washing, being dried, and filtrate is processed by the method for flash distillation.These two kinds of methods not only all exist needs multi-work-station operation, resulting PPS product in these operating process inevitably with environmental exposure, affect and reduced the performance of product, also can phase mutual interference between different solvents in treating processes, and solvent load is large, complex operation.
In addition, EP 1452555A1 has also reported a kind of continuous washing method to polyarylene sulfide (PAS), by lower to pipe and in the equipment that forms of pipe, slurry is entered to pipe from lower, washing lotion is entered to pipe by upper, by washing lotion and slurry, under countercurrent washing and slurry, enter the sedimentation in process, by removals such as the by product in PAS, auxiliary agents.But the washing speed of this method is slow, low to the efficiency of output on PAS particle, and device is complicated, is unfavorable for disassembly, cleaning.
Summary of the invention
Given this, the invention provides a kind of p-poly-phenyl thioether (PPS) resin slurry, particularly, to completing the treatment process of the reactant slurry after polyreaction under participating at N-Methyl pyrrolidone (NMP) reaction medium catalyst neutralisation lithium chloride, can address the above problem satisfactorily.
The primary process of polyphenylene sulfide slurry treatment process of the present invention, under N-Methyl pyrrolidone reaction medium and the participation of catalyzer lithium chloride, to complete the reactant slurry of polyreaction, under the condition lower than polymeric reaction temperature after solid-liquid separation, residual solvent remove solid substance at 180 ~ 240 ℃ in, obtain the solid substance containing polyphenylene sulfide product, carry out respectively again and all complete following operations, obtaining the polyphenylene sulfide product of purifying:
Operation A: by solid substance 80 ~ 200 ℃ and regulation system pH value to 6-7.5 condition, after disperseing in organic amide and/or lactan solvent and washing, solid-liquid separation, remove solvent residual in solid substance being not less than under the condition of described solvent boiling point, obtain the solid substance containing polyphenylene sulfide product.The described organic amide as cleaning solvent and/or lactan, can comprise as conventional N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, N, N-diethyl acetamide, N-Methyl pyrrolidone, N-ethyl pyrrolidone, N-n-propyl pyrrolidone, N-n-butylpyrrolioine ketone etc., wherein preferably adopt with reaction medium solvent phase with N-Methyl pyrrolidone, to reduce, adopt the intersection of the different solvents that other solvent wash causes to be mixed into follow-up solvent recuperation and cause difficulty.
Operation B: by solid substance can be with N-Methyl pyrrolidone miscible and boiling point disperse after washing in lower than the low boiling point organic solvent of 100 ℃, solid-liquid separation, remove solvent residual in solid substance being not less than under the condition of described solvent boiling point, obtain the solid substance containing polyphenylene sulfide product.
Operation C: by solid substance lower than 100 ℃, disperses to wash in being preferably the aqueous solution of temperature 60-90 ℃ after, solid-liquid separation, under being not less than the condition of described solvent boiling point, remove the residual solvent in solid substance, obtain the solid substance containing polyphenylene sulfide product.Wherein, after solid-liquid separation, under being not less than described solvent boiling point condition, remove solid substance in the temperature of residual solvent, be preferably 110-140 ℃.
In above-mentioned operations, to the order of presentation of operations, generally can have no special requirements.Therefore, the initial solid substance described in every operation, be respectively its actual described corresponding solid substance containing polyphenylene sulfide product of drilling and obtaining after doing to finish of accepting.
In reaction product slurry after polyreaction completes, inevitably contain the compositions such as a large amount of mineral ions and oligopolymer, the above-mentioned treatment process of the present invention is for character and the feature of these dissimilar impurity, by above-mentioned operations, these impurity components can progressively be removed respectively effectively.For example, wherein said operation A, can mainly remove the oligopolymer and the catalyzer lithium chloride that mix in PPS product; Described operation B, mainly can remove the impurity components such as solvent NMP remaining in resin, a small amount of moisture, lower-molecular substance and part coloring matter; Described operation C, can mainly remove the inorganic salt compositions such as sodium-chlor that mix in PPS resin.
Due to the operations described in aforesaid method of the present invention mainly for be the impurity of different properties, feature, therefore after described operations being carried out respectively and all completing, the different impurities composition mixing after polyreaction in resulting PPS resin can be removed totally, be obtained the PPS resin product of purifying.Putting before this, to the carrying out of described operations with complete order, do not needing too much restriction necessary.But from actual production, can enter a convenience and simplify the operation, and the comprehensive utilization to resource compositions such as the raw material of separated removal, reagent, solvent/solution in treating processes, and reduce the pollution of environment etc. is considered, in above-mentioned treatment process of the present invention, described in being obtained by the reactant slurry that completes polyreaction, remove the solid substance containing polyphenylene sulfide product after residual solvent, preferred mode, be according to by operation A to operation B, finally for the order of operation C is carried out successively and complete described operations.Wherein, by described, complete reactant slurry after polyreaction through the resulting liquid composition of solid-liquid separation, and at 180 ~ 240 ℃, further remove remain in the solvent in solid substance, be recovered and all can return in polyreaction and be recycled as reaction medium solvent afterwards; In said operations, by after removed solvent or solution recovery, also can turn back to respectively in corresponding operation steps and be recycled as cleaning solvent or solution.
In the above-mentioned treatment process of the present invention, the solid-liquid separation in described each link, all preferably adopts by automatic filter currently reported and/or that use and automatically carries out; And, by starting completing the solid-liquid separation that the reactant slurry of polyreaction carries out, all complete to described operations, preferably employing is carried out in a continuous manner, for example, can adopt in many oars of tandem multiple-grooved rinse bath of removable form and carry out continuously.The advantage of many oars of tandem multiple-grooved rinse bath of removable form, to regulate according to the needs of washing the joint number of the series connection washing trough being used in combination, suitable/contrary commutation agitator treating repeatedly of connecting by multiple-grooved, can control and make to be washed that material fully disperses and the residence time in washing trough is consistent, the contact area of material and cleaning solvent/solution is larger, mass-and heat-transfer efficiency and to wash efficiency also higher, the usage quantity of solvent relatively still less.
In addition, more preferably, by completing reactant slurry after polyreaction, carry out described solid-liquid separation and start, to described operations, all adopt under the sealing condition with outside air isolation and carry out and complete, to avoid the contacting disadvantageous effect causing product performance with outside air.
On the basis of above-mentioned treatment process, can also be separately or the further preferred embodiment that adopts of arbitrary combination comprise:
To the described solid-liquid separation that completes the reactant slurry after polyreaction, preferably under 150 ~ 240 ℃ of conditions a little less than polymeric reaction temperature, carry out, it is separated to greatest extent that the lithium chloride that is conducive to enable to be dissolved in NMP and oligopolymer and the inorganic salt such as insoluble PPS resin and sodium-chlor obtain, and to facilitate by follow-up operations, removed respectively.
Above-mentioned to completing after polyreaction, the operation of removing residual solvent in the solid substance being obtained through solid-liquid separation by described reactant slurry, can be preferably at 203 ~ 240 ℃, particularly at 210 ℃-240 ℃, be not less than under the temperature condition of NMP boiling point, in flash distillation mode (as in vacuum flashing moisture eliminator), remove nmp solvent residual in solid substance.Make fluid in the equipment such as flash tank by flash distillation, can make seethe with excitement rapidly vaporization and realize two-phase sharp separation of liquid.
In like manner, in described operations, the solid substance after disperseing washing and solid-liquid separation equally also, preferably in the mode of flash distillation, under the condition of cleaning solvent boiling point used, is removed cleaning solvent residual in solid substance or solution in being not less than described operation.
Experiment shows, in the operation A of above-mentioned treatment process, to described solid substance, when system pH is the dispersion washing under 6-7.5 condition, preferred temperature is 80 ~ 120 ℃, when catalyzer lithium chloride can fully be dissolved, also reduced to greatest extent the loss of solvent NMP.
In operation B described in above-mentioned treatment process, for described solid substance is disperseed washing can be miscible with N-Methyl pyrrolidone low boiling point organic solvent, preferably boiling point is that 40-80 ℃, particularly boiling point are the low boiling point organic solvent of 40-60 ℃.For example, can select to comprise at least one in the conventional low boiling point solvents such as methyl alcohol, ethanol, acetone.
Experimental result shows, the above-mentioned treatment process of the present invention, can effectively reduce the content of oligopolymer contained in polyphenylene sulfide, inorganic salt and other impurity, purity is high, ash oontent is low, color and luster is good, also greatly reduces the consumption to cleaning solvent, has also avoided the interference between the solvent of each section of washing.In addition, by aforesaid method of the present invention, be also appreciated that, whole treating processes can realize carrying out continuously under sealing condition easily, without manual operation, thereby significantly reduced cost, improved processing efficiency, also effectively avoided product in treating processes because of with environmental exposure to causing the disadvantageous effect to performance, simultaneously can there is obvious economic benefit and environmental benefit.
Embodiment is by the following examples described in further detail foregoing of the present invention again.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following example.Without departing from the idea case in the present invention described above, various replacements or the change according to ordinary skill knowledge and customary means, made, all should comprise within the scope of the invention.
Embodiment
Take sodium sulphite and santochlor as raw material, under N-Methyl pyrrolidone (NMP) reaction medium solvent catalyst neutralisation lithium chloride exists, through dehydration polycondensation, complete after the polyreaction of polyphenylene sulfide (PPS) resin, reactant slurry is processed by following embodiment respectively.
embodiment 1
PPS resin slurry is continuous in automatic filter at 150 ℃, wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 210 ℃, dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the many oars of screw input feeder input first paragraph closed multiple-grooved tandem washing trough capable of being combined, filtrate and the phlegma being reclaimed by flash distillation are collected to storage tank, the PPS polyreaction for lower batch capable of circulation.
Using the NMP washings of 80 ℃ and adjust conventional mineral acid (hydrochloric acid, sulfuric acid, phosphoric acid etc.) that pH uses inject simultaneously this first again stock tank as washings, regulate washings pH value to be about 6.In many oars of the closed multiple-grooved tandem washing trough being become by 4 joint series combinations, the filter cake that washings and the first step are obtained forms and flows and disperseed fully and wash 40min.Because a dried filter cake moisture content is few, lithium chloride and oligopolymer major part dissolve in NMP washings, the inorganic salt such as poly-PPS resin and sodium-chlor are insoluble to NMP, in order to follow-up washing, are mainly desalinations.Material is through final section again after stock tank, input automatic filter, wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 210 ℃, dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the many oars of screw input feeder input second segment closed multiple-grooved tandem washing trough capable of being combined, the phlegma of wash filtrate and flash distillation is collected to storage tank, capable of circulation for washing.
Temperature is injected to the first stock tank again of the many oars of closed multiple-grooved of the second washing section tandem washing trough capable of being combined lower than the ethanol of 40 ℃ (or methyl alcohol, acetone etc. at least one) low boiling point solvent, the dry cake obtaining with second step forms and flows, and fully disperses and washing 40min at the series combination by 4 joint combinations in many oars of the closed multiple-grooved tandem washing trough becoming.Residual low-molecular(weight)polymer, oligopolymer and catalyzer lithium chloride etc. in filter cake, suitable, the counter-clockwise agitator treating by each stirring rake is dissolved in washings, and through final section, again after stock tank, input automatic filter filters.Wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 100 ℃.Dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the 3rd section of many oars of closed multiple-grooved of screw input feeder input tandem washing trough capable of being combined.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washing soln that is used as the second washing section capable of circulation.
By the deionization of 60 ℃ inject the many oars of closed multiple-grooved of the 3rd washing section tandem washing groove capable of being combined first again stock tank (can add sodium-acetate, or Lithium Acetate, Potassium ethanoate etc., regulate pH ≈ 7, to adjust back the impact of pH in upper step), to remove most salt in resin slurry.The filter cake that washing lotion and upper step obtain forms and flows, and fully disperses and washing 40min at the series combination being combined into by 4 joints in many oars of the closed multiple-grooved tandem washing trough becoming.The inorganic salt such as residual sodium-chlor and a small amount of lithium chloride in filter cake, are dissolved in washings through suitable, the counter-clockwise agitator treating of each stirring rake, through final section again after stock tank, and input automatic filter.Wet cake enters vacuum flashing moisture eliminator, expansion drying at 110 ℃ through screw input feeder.According to the impurity detection case in filter cake after washing, dried filter cake (containing the solid substance of polyphenylene sulfide product) can continue the first stock tank again through the tandem washing trough capable of being combined of the 4th section of many oars of closed multiple-grooved of screw input feeder input.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washings that is used as the 3rd section capable of circulation.
By the first stock tank again of the tandem washing groove that the deionized water of 60 ℃ injects the 4th washing section, the many oars of closed multiple-grooved that are comprised of 6 joints series connection washing troughs are capable of being combined, control slurry and disperse washing stop 60min.Slurry is through final section again after stock tank, and input automatic filter filters.Wet cake enters vacuum flashing moisture eliminator, expansion drying at 110 ℃, the dry PPS product after being purified through screw input feeder.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washings that is used as the 4th washing section capable of circulation.
By above-mentioned steps, processed and can be obtained highly purified white polyphenylene sulfide, purity detecting result is as shown in table 1." conventional treatment method " described in table, can be with reference to the research > > (plastics industry of < < polyphenylene sulfide synthesis technique, the 39th 7 phases of volume, in July, 2011) mode in, adopts deionized water wash.The method is when the factor condition that washing time, temperature, the water yield etc. is affected to washing effect is controlled at optimum regime, the result of its report can only be by ash control at 0.6 ~ 0.7%(wt), the rear resin that adopts the inventive method to process, the general control scope of ash content can <0.27%(wt).
Detection method: polyphenylene sulfide, at 800 ℃ of retort furnace calcination 8h, then, with the residue in the dry pot of deionized water dissolving, is used Atomic Absorption Spectrometry cations; Polyphenylene sulfide boils backflow 24h with deionized water, adopts ion chromatography anion-content.With methylene dichloride extracting 24h, then dry in apparatus,Soxhlet's, weigh, measure oligomer.
The polyphenylene sulfide purity detecting result that table 1 different treatment method obtains
| Sample | The polyphenylene sulfide that ordinary method is processed | The polyphenylene sulfide that present method is processed |
| Sodium ions content (ppm) | >1200 | <80 |
| Lithium ion content (ppm) | >100 | <15 |
| Chloride ion content (ppm) | >1300 | <95 |
| Oligopolymer (w%) | 5 | 0.5 |
embodiment 2
PPS resin slurry is continuous in automatic filter at 195 ℃, wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 225 ℃, dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the many oars of screw input feeder input first paragraph closed multiple-grooved tandem washing trough capable of being combined, filtrate and the phlegma being reclaimed by flash distillation are collected to storage tank, the PPS polyreaction for lower batch capable of circulation.
Using the NMP washings of 100 ℃ and adjust conventional mineral acid (hydrochloric acid, sulfuric acid, phosphoric acid etc.) that pH uses inject simultaneously this first again stock tank as washings, regulate washings pH value to be about 6.In many oars of the closed multiple-grooved tandem washing trough being become by 6 joint series combinations, the filter cake that washings and the first step are obtained forms and flows and disperseed fully and wash 60min.Because a dried filter cake moisture content is few, lithium chloride and oligopolymer major part dissolve in NMP washings, the inorganic salt such as poly-PPS resin and sodium-chlor are insoluble to NMP, in order to follow-up washing, are mainly desalinations.Material is through final section again after stock tank, input automatic filter, wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 225 ℃, dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the many oars of screw input feeder input second segment closed multiple-grooved tandem washing trough capable of being combined, the phlegma of wash filtrate and flash distillation is collected to storage tank, the washing soln that is used as the first washing section capable of circulation.
At least one low boiling point solvent in acetone or methyl alcohol is injected to the first stock tank again of the many oars of closed multiple-grooved of the second washing section tandem washing trough capable of being combined, the dry cake obtaining with second step forms and flows, and fully disperses and washing 60min at the series combination by 6 joint combinations in many oars of the closed multiple-grooved tandem washing trough becoming.Residual low-molecular(weight)polymer, oligopolymer and catalyzer lithium chloride etc. in filter cake, suitable, the counter-clockwise agitator treating by each stirring rake is dissolved in washings, and through final section, again after stock tank, input automatic filter filters.Wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 110 ℃.Dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the 3rd section of many oars of closed multiple-grooved of screw input feeder input tandem washing trough capable of being combined.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washing soln that is used as the second washing section capable of circulation.
By the deionization of 75 ℃ inject the many oars of closed multiple-grooved of the 3rd washing section tandem washing groove capable of being combined first again stock tank (can add sodium-acetate, or Lithium Acetate, Potassium ethanoate etc. regulate pH ≈ 7), remove most salt in resin slurry, the filter cake that washing lotion and the 3rd step obtain forms and flows, and fully disperses and washing 80min at the series combination being combined into by 8 joints in many oars of the closed multiple-grooved tandem washing trough becoming.The inorganic salt such as residual sodium-chlor and a small amount of lithium chloride in filter cake, are dissolved in washings through suitable, the counter-clockwise agitator treating of each stirring rake, through final section again after stock tank, and input automatic filter.Wet cake enters vacuum flashing moisture eliminator, expansion drying at 125 ℃ through screw input feeder.According to the impurity detection case in filter cake after washing, dried filter cake (containing the solid substance of polyphenylene sulfide product) can continue the first stock tank again through the tandem washing trough capable of being combined of the 4th section of many oars of closed multiple-grooved of screw input feeder input.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washings that is used as the 3rd section capable of circulation.
By the first stock tank again of the tandem washing groove that the deionized water of 75 ℃ injects the 4th washing section, the many oars of closed multiple-grooved that are comprised of 9 joints series connection washing troughs are capable of being combined, control slurry and disperse washing stop 90min.Slurry is through final section again after stock tank, and input automatic filter filters.Wet cake enters vacuum flashing moisture eliminator, expansion drying at 125 ℃, the dry PPS product after being purified through screw input feeder.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washings that is used as the 4th washing section capable of circulation.
By above-mentioned steps, process and can obtain highly purified white polyphenylene sulfide, adopt the purity detecting result of embodiment 1 same detection method as shown in table 2.
The polyphenylene sulfide purity detecting result that table 2 different treatment method obtains
| Sample | The polyphenylene sulfide that ordinary method is processed | The polyphenylene sulfide that present method is processed |
| Sodium ions content (ppm) | >1200 | <55 |
| Lithium ion content (ppm) | >100 | <10 |
| Chloride ion content (ppm) | >1300 | <65 |
| Oligopolymer (w%) | 5 | 0.3 |
embodiment 3
PPS resin slurry is continuous in automatic filter at 240 ℃, wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 240 ℃, dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the many oars of screw input feeder input first paragraph closed multiple-grooved tandem washing trough capable of being combined, filtrate and the phlegma being reclaimed by flash distillation are collected to storage tank, the PPS polyreaction for lower batch capable of circulation.
Using the NMP washings of 120 ℃ and adjust conventional mineral acid (hydrochloric acid, sulfuric acid, phosphoric acid etc.) that pH uses inject simultaneously this first again stock tank as washings, regulate washings pH value to be about 6.In many oars of the closed multiple-grooved tandem washing trough being become by 8 joint series combinations, the filter cake that washings and the first step are obtained forms and flows and disperseed fully and wash 100min.Because a dried filter cake moisture content is few, lithium chloride and oligopolymer major part dissolve in NMP washings, the inorganic salt such as poly-PPS resin and sodium-chlor are insoluble to NMP, in order to follow-up washing, are mainly desalinations.Material is through final section again after stock tank, input automatic filter, wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 240 ℃, dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the many oars of screw input feeder input second segment closed multiple-grooved tandem washing trough capable of being combined, the phlegma of wash filtrate and flash distillation is collected to storage tank, the washing soln that is used as the first washing section capable of circulation.
At least one low boiling point solvent such as ethanol is injected to the first stock tank again of the many oars of closed multiple-grooved of the second washing section tandem washing trough capable of being combined, the dry cake obtaining with second step forms and flows, and fully disperses and washing 80min at the series combination by 8 joint combinations in many oars of the closed multiple-grooved tandem washing trough becoming.Residual low-molecular(weight)polymer, oligopolymer and catalyzer lithium chloride etc. in filter cake, suitable, the counter-clockwise agitator treating by each stirring rake is dissolved in washings, and through final section, again after stock tank, input automatic filter filters.Wet cake enters vacuum flashing moisture eliminator through screw input feeder, expansion drying at 120 ℃.Dried filter cake (containing the solid substance of polyphenylene sulfide product) is through the first stock tank again of the 3rd section of many oars of closed multiple-grooved of screw input feeder input tandem washing trough capable of being combined.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washing soln that is used as the second washing section capable of circulation.
By the deionization of 90 ℃ inject the many oars of closed multiple-grooved of the 3rd washing section tandem washing groove capable of being combined first again stock tank (can add Potassium ethanoate, or sodium-acetate, Potassium ethanoate etc., regulate pH ≈ 7), remove most salt in resin slurry, the filter cake that washing lotion and the 3rd step obtain forms and flows, and fully disperses and washing 80min at the series combination being combined into by 8 joints in many oars of the closed multiple-grooved tandem washing trough becoming.The inorganic salt such as residual sodium-chlor and a small amount of lithium chloride in filter cake, are dissolved in washings through suitable, the counter-clockwise agitator treating of each stirring rake, through final section again after stock tank, and input automatic filter.Wet cake enters vacuum flashing moisture eliminator, expansion drying at 120 ℃ through screw input feeder.According to the impurity detection case in filter cake after washing, dried filter cake (containing the solid substance of polyphenylene sulfide product) can continue the first stock tank again through the tandem washing trough capable of being combined of the 4th section of many oars of closed multiple-grooved of screw input feeder input.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washings that is used as the 3rd section capable of circulation.
By the first stock tank again of the tandem washing groove that the deionized water of 90 ℃ injects the 4th washing section, the many oars of closed multiple-grooved that are comprised of 12 joints series connection washing troughs are capable of being combined, control slurry and disperse washing stop 120min.Slurry is through final section again after stock tank, and input automatic filter filters.Wet cake enters vacuum flashing moisture eliminator, expansion drying at 140 ℃, the dry PPS product after being purified through screw input feeder.The phlegma that wash filtrate and flash distillation are collected is collected to storage tank, the washings that is used as the 4th washing section capable of circulation.
By above-mentioned steps, process and can obtain highly purified white polyphenylene sulfide, adopt the purity detecting result of embodiment 1 same detection method as shown in table 3.
The polyphenylene sulfide purity detecting result that table 3 different treatment method obtains
| Sample | The polyphenylene sulfide that ordinary method is processed | The polyphenylene sulfide that present method is processed |
| Sodium ions content (ppm) | >1200 | <35 |
| Lithium ion content (ppm) | >100 | <6 |
| Chloride ion content (ppm) | >1300 | <40 |
| Oligopolymer (w%) | 5 | 0.2 |
Claims (10)
1. the treatment process of polyphenylene sulfide slurry, it is characterized in that under N-Methyl pyrrolidone reaction medium and the participation of catalyzer lithium chloride, completing the reactant slurry of polyreaction, solid-liquid separation under the condition lower than polymeric reaction temperature, and remove the residual solvent in solid substance under 180 ~ 240 ℃ of conditions, obtain the solid substance containing polyphenylene sulfide product, then carry out respectively and complete following operations, obtain the polyphenylene sulfide product of purifying, the initial solid substance described in every operation wherein, the described solid substance containing polyphenylene sulfide product obtaining after doing to finish for its drilling of accepting:
Operation A: by solid substance 80 ~ 200 ℃ and regulation system pH value to 6-7.5 condition, in organic amide and/or lactan solvent, preferably in N-Methyl pyrrolidone solvent, disperse after washing, solid-liquid separation, under being not less than the condition of described solvent boiling point, remove the residual solvent in solid substance, obtain the solid substance containing polyphenylene sulfide product;
Operation B: by solid substance can be with N-Methyl pyrrolidone miscible and boiling point disperse after washing in lower than the low boiling point organic solvent of 100 ℃, solid-liquid separation, under being not less than the condition of described solvent boiling point, remove the residual solvent in solid substance, obtain the solid substance containing polyphenylene sulfide product;
Operation C: by solid substance lower than 100 ℃, disperses to wash in being preferably the aqueous solution of temperature 60-90 ℃ after, solid-liquid separation, be not less than described solvent boiling point, preferably under 110-140 ℃ of condition, removing the residual solvent in solid substance, obtaining the solid substance containing polyphenylene sulfide product.
2. treatment process as claimed in claim 1, described in it is characterized in that, complete after the reactant slurry solid-liquid separation of polyreaction, at 203 ~ 240 ℃, preferably under 210 ℃ of-240 ℃ of conditions, remove solvent residual in solid substance, obtain the described solid substance containing polyphenylene sulfide product.
3. treatment process as claimed in claim 1, described in it is characterized in that being obtained by the reactant slurry that completes polyreaction, remove the solid substance containing polyphenylene sulfide product after residual solvent, according to by operation A to operation B, finally for the order of operation C is carried out successively and complete described operations.
4. treatment process as claimed in claim 2, solid-liquid separation described in it is characterized in that is through automatic filter and automatically completes, and by carrying out solid-liquid separation and start completing the reactant slurry of polyreaction, extremely described operations all completes, for carrying out in a continuous manner, preferably in many oars of tandem multiple-grooved rinse bath of removable form, carry out continuously.
5. the treatment process as described in one of claim 1 to 4, is characterized in that carrying out described solid-liquid separation and starting by completing reactant slurry after polyreaction, to described operations, all under the sealing condition of isolating with outside air, carries out.
6. treatment process as claimed in claim 5, is characterized in that the described solid-liquid separation that completes the reactant slurry after polyreaction to carry out under 150 ~ 240 ℃ of temperature condition.
7. treatment process as claimed in claim 5, is characterized in that the residual solvent in the solid substance after described solid-liquid separation, all adopts flash distillation mode to remove.
8. treatment process as claimed in claim 5, is characterized in that in described operation A to described solid substance being that dispersion wash temperature under 6-7.5 condition is 80 ~ 120 ℃ in system pH.
9. treatment process as claimed in claim 5, it is characterized in that in described operation B for described solid substance is disperseed wash can be miscible with N-Methyl pyrrolidone solvent be that boiling point is 40-80 ℃, preferably boiling point is the low boiling point organic solvent of 40-60 ℃.
10. treatment process as claimed in claim 9, is characterized in that described low boiling point organic solvent is at least one in methyl alcohol, ethanol, acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410328177.4A CN104072772A (en) | 2014-07-11 | 2014-07-11 | Treatment method for polyphenylene sulfide resin slurry |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410328177.4A CN104072772A (en) | 2014-07-11 | 2014-07-11 | Treatment method for polyphenylene sulfide resin slurry |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104072772A true CN104072772A (en) | 2014-10-01 |
Family
ID=51594401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410328177.4A Pending CN104072772A (en) | 2014-07-11 | 2014-07-11 | Treatment method for polyphenylene sulfide resin slurry |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104072772A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254889A (en) * | 2015-11-11 | 2016-01-20 | 成都惠恩精细化工有限责任公司 | High-purity linear polyarylene sulfide and synthesis method and application thereof |
| CN105568694A (en) * | 2016-03-09 | 2016-05-11 | 广东工业大学 | Thermoplastic sizing agent and preparation method and application thereof |
| CN110527089A (en) * | 2019-07-31 | 2019-12-03 | 长治市霍家工业有限公司 | A kind of purification process producing high-purity polyphenylene sulfide |
| CN113680128A (en) * | 2021-07-27 | 2021-11-23 | 山东明化新材料有限公司 | Continuous washing and purifying system and purifying method for polyarylene sulfide resin |
| CN114008112A (en) * | 2019-06-28 | 2022-02-01 | 提克纳有限责任公司 | Method of forming polyarylene sulfide |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507468A (en) * | 1982-07-16 | 1985-03-26 | Dainippon Ink And Chemicals, Inc. | Method for purifying polyphenylene sulfide |
| JP2000136246A (en) * | 1998-11-02 | 2000-05-16 | Dainippon Ink & Chem Inc | Purification of polyarylene sulfide |
| CN1597736A (en) * | 2004-08-24 | 2005-03-23 | 四川大学 | Purification method of polyphenyl thioether |
| CN1624023A (en) * | 2004-11-02 | 2005-06-08 | 四川省纺织工业研究所 | Process for purification refine of macromolecular weight poly benzene thioether resin |
| JP2007262341A (en) * | 2006-03-30 | 2007-10-11 | Toray Ind Inc | Purification method of polyarylene sulfide resin |
| CN102219904A (en) * | 2011-06-07 | 2011-10-19 | 四川宝利丰科技有限公司 | Polyphenylene sulfide resin purifying method |
| CN102675641A (en) * | 2011-03-18 | 2012-09-19 | 四川得阳工程塑料开发有限公司 | Product purification treatment process for polyphenylene sulfide production |
| CN102731785A (en) * | 2012-06-11 | 2012-10-17 | 张家港市新盛新材料有限公司 | Polyphenylene sulfide purifying method |
-
2014
- 2014-07-11 CN CN201410328177.4A patent/CN104072772A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4507468A (en) * | 1982-07-16 | 1985-03-26 | Dainippon Ink And Chemicals, Inc. | Method for purifying polyphenylene sulfide |
| JP2000136246A (en) * | 1998-11-02 | 2000-05-16 | Dainippon Ink & Chem Inc | Purification of polyarylene sulfide |
| CN1597736A (en) * | 2004-08-24 | 2005-03-23 | 四川大学 | Purification method of polyphenyl thioether |
| CN1624023A (en) * | 2004-11-02 | 2005-06-08 | 四川省纺织工业研究所 | Process for purification refine of macromolecular weight poly benzene thioether resin |
| JP2007262341A (en) * | 2006-03-30 | 2007-10-11 | Toray Ind Inc | Purification method of polyarylene sulfide resin |
| CN102675641A (en) * | 2011-03-18 | 2012-09-19 | 四川得阳工程塑料开发有限公司 | Product purification treatment process for polyphenylene sulfide production |
| CN102219904A (en) * | 2011-06-07 | 2011-10-19 | 四川宝利丰科技有限公司 | Polyphenylene sulfide resin purifying method |
| CN102731785A (en) * | 2012-06-11 | 2012-10-17 | 张家港市新盛新材料有限公司 | Polyphenylene sulfide purifying method |
Non-Patent Citations (1)
| Title |
|---|
| 管从胜: "《聚苯硫醚涂料及应用》", 31 May 2007, 化学工业出版社 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105254889A (en) * | 2015-11-11 | 2016-01-20 | 成都惠恩精细化工有限责任公司 | High-purity linear polyarylene sulfide and synthesis method and application thereof |
| CN105254889B (en) * | 2015-11-11 | 2017-07-18 | 成都惠恩精细化工有限责任公司 | A kind of linear poly arylidene thio-ester of high-purity and its synthetic method and application |
| CN105568694A (en) * | 2016-03-09 | 2016-05-11 | 广东工业大学 | Thermoplastic sizing agent and preparation method and application thereof |
| CN114008112A (en) * | 2019-06-28 | 2022-02-01 | 提克纳有限责任公司 | Method of forming polyarylene sulfide |
| CN110527089A (en) * | 2019-07-31 | 2019-12-03 | 长治市霍家工业有限公司 | A kind of purification process producing high-purity polyphenylene sulfide |
| CN110527089B (en) * | 2019-07-31 | 2022-02-18 | 长治市霍家工业有限公司 | Purification method for producing high-purity polyphenylene sulfide resin |
| CN113680128A (en) * | 2021-07-27 | 2021-11-23 | 山东明化新材料有限公司 | Continuous washing and purifying system and purifying method for polyarylene sulfide resin |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104072772A (en) | Treatment method for polyphenylene sulfide resin slurry | |
| KR20160110548A (en) | Polyarylene sulfide production method, and polyarylene sulfide production apparatus | |
| CN102864672B (en) | Method for extracting lignin | |
| CN102993078A (en) | Method for purifying N-methyl pyrrolidone | |
| CN107337618B (en) | Production method for simultaneously improving purity and yield of metformin hydrochloride | |
| CN106565956A (en) | Method for comprehensive recycling of by-product slurry in polyphenylene sulfide productive process | |
| CN109111410A (en) | A kind of processing method of acid-base method 2-mercaptobenzothiazole production waste material | |
| CN106395862B (en) | The recovery method of byproduct sodium chloride in a kind of polyphenylene sulfide production process | |
| CN104761452B (en) | A kind of purification process of butyl acrylate coarse product | |
| CN102634011B (en) | Poly-p-phenylene terephthamide (PPTA) polymer washing and solvent recovery method | |
| CN104892971B (en) | Method for recycling solvent NMP in polyphenylene sulfide resin production process | |
| CN113248385B (en) | Method for reducing alkali consumption of acidic nitrobenzene | |
| CN104592160B (en) | Method for multistage washing impurity removal of rubber vulcanizing accelerator TBBS | |
| CN102491575A (en) | Method for performing comprehensive treatment by utilizing waste water from production of ternary monomer | |
| CN101134824A (en) | Method for reclaiming solvent from aramid fiber polymeric compound | |
| CN100475797C (en) | Method of obtaining 2-mercaptobenzothiazole | |
| CN104003910A (en) | Method for extracting m-phthalic acid-5-sodium sulfonate from ternary-monomer industrial waste water | |
| CN104496820A (en) | Preparation method of light stabilizer 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate | |
| CN106380601A (en) | Purifying method for polyphenylene sulfide with high molecular weight | |
| CN105037082A (en) | Method for recycling paradichlorobenzene in polyphenylene sulphide production mother liquor | |
| CN113680128B (en) | Continuous washing and purifying system and purifying method for polyarylene sulfide resin | |
| CN105503690A (en) | High-concentration N-phenylmaleimide reaction liquid post-treatment process | |
| CN107936288A (en) | A kind of method of NMP and LiCl in the recycling polyphenylene sulfide production by solvent extraction process technology | |
| CN104086406B (en) | A kind of from the method containing Separation and Recovery sodium oxalate the waste water of oxalic acid | |
| CN203269569U (en) | Sulfamic acid preparation device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20141001 |