CA1312411C - Process for the purification of polyarylene sulphides - Google Patents
Process for the purification of polyarylene sulphidesInfo
- Publication number
- CA1312411C CA1312411C CA000564825A CA564825A CA1312411C CA 1312411 C CA1312411 C CA 1312411C CA 000564825 A CA000564825 A CA 000564825A CA 564825 A CA564825 A CA 564825A CA 1312411 C CA1312411 C CA 1312411C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- sulphide
- polyarylene
- polyarylene sulphide
- stands
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0277—Post-polymerisation treatment
- C08G75/0281—Recovery or purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0209—Polyarylenethioethers derived from monomers containing one aromatic ring
- C08G75/0213—Polyarylenethioethers derived from monomers containing one aromatic ring containing elements other than carbon, hydrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
Process for the purification of polyarylene sulphides A b s t r a c t This invention relates to a process for the purification of a polyarylene sulphide with reduction in the amount of ash-forming impurities contained therein, which process comprises demoisturizing a moist polyarylene sulphide under a high pressure with concomitant application of shearing force. Polyarylene sulphides which have been purified according to the invention are distinguished by the reduced amount of ash-forming impurities contained in them.
Description
~312~
Process for the purification of polyarylene sulphides This invention relates to a process for the purification of optionally branched polyarylene sulphides (PPS).
Polyarylene sulphides which have been purified according to the invention are distinguished by the reduced amount of ash-forming impurities contained in them.
Polyarylene sulphides and processes for their prepara-tion and isolation are known (e.g. US-P 4 071 509, JA-P 57 108-135, DE-OS 3 143 992, US-P 3 354 129, 3 457 242, 3 478 000, 3 687 907, 3 707 52~, 3 839 302, 3 941 664, 3 956 060, 4 046 749 and 4 178 435 and EP 79 144).
It is known, for example~that the solvent in which the polymerisation of the halogenated aromatic compounds and the source of sulphur was carried out may be evaporated from the reaction mixture and the inorganic salts may then be washed out of the remaining residue. Alternatively, the reaction mixture obtained after the polymerisation reaction may be immediately introduced into water without removal of the solvent and the precipitated residue may then be separated and washed. It is also known to wash the residue with organic solvents such as acetone, aromatic hydrocarbons, dimethylsulphoxide (DMSO) and N-methyl-pyrrolidone (NMP).
Polyarylene sulphides may also be purified by, for example, heating them in water with alkali metal acetates to temperatures just below their melting point (DE-OS
3 143 992), or by extraction with solvent mixtures s~ch as N-methylpyrrolidone and ethylene glycol (JA-P 57 108-135) or by heating them in organic amides in the presence of Le A 25 187 13~2~1~
certain alkali metal salts (US-P 4 071 509), etc.
The amount of ash-forming impurities in PPS 'may also be reduced by treatment of the aqueus PPS suspensions with atmospheric oxygen at temperatures above 200C but this may be accompanied by uncontrolled branching or cross-linking of the product (US-P 4 376 190).
Purified PPS has a lower concentration of ash-forming impurities and splits off a smaller amount of volatile compounds when processed and therefore causes less corrosion to the tools and apparatus used for its processes.
Furthermore, impurities left in PPS are liable to be troublesome when polyarylene sulphides are used for electric-al parts.
It has been found that the amount of ash-forming impurities contained in PPS can be considerably reduced if moist polyarylene sulphides obtained, for example, after they~have been washed to extract the soluble impur-ities in the process for their preparation~are demoisturised under a high pre~sure while subjected to shearing f~rces, e.g. in suitable pressure belts or between pressure rollers.
The present invention relates to a process for the purification of polyarylene sulphides with reduction of the quantity of ash-forming impurities, characterised in that moist polyarylene sulphides are demoisturised under a high pressure with concomitant application of shearing forces.
The process according to the invention may be used for treating, for example, straight chained or branched polyarylene sulphides which have been prepared by, for example, the known reaction of a~ 50 to 100 mol-% of dihalogenated aromatic compounds of the formula H
h - ~ (I), ~X ~
H H ~
Le A 25 187 2 ~
3L 3 ~
and 0 to 50 mol-% of dihalogenated aromatic compounds of the formula ~ R
X - ~ tII), wherein S X stands for halogens such as chlorine or bromine in the meta- or para-position to one another and R1 stands for identical or different groups and may denote hydrogen, alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl or two groups R1 in the ortho-position to one another may be linked together to form an aromatic or heterocyclic ring, and b) 0 to 5 mol-%, preferably 0.05 to 2.S mol-%, based on the sum of the dihalogenated aromatic compounds of formulae (I) and (II), of a tri- or tetra-halogenated aromatic compound of the formula ArXn (III) wherein Ar denotes an aromatic or heterocyclic group, X stands for a halogen such as chlorine or bromine and n stands for the number 3 or 4, and c) alkali metal sulphides, preferably sodium or potassium sulphide or mixtures thereof, preferably in the form of their hydrates or aqueous mixtures, optionally together with alkali metal hydroxides such as sodium or potassum hydroxide, the molar ratio of (a+b):c being in the range of from 0.85:1 to 1.15:1, preferably from 0.90:1 to 1.05:1, in d) organic solvents, preferably N-alkyl-lactams or peralkylated ureas, optionally with the addition of catalysts and/or cosolvents, using a molar ratio of alkali metal sulphides c) to organic solvents d) Le A 25 187 1312~ ~
in the range of from 1:2 to 1:15, and e) water in the form of water of hydration or free water, the molar ratio of c:d being in the range of from 1:0 to 1:6, at a reaction temperature of from 160GC
to 270C, optionally under excess pressure.
The reaction mixture obtained may be introduced into a precipitating agent after the polymerisation reaction.
The soluble impurities may be washed out of the precipitated polyarylene sulphide with water and/or some other extracting agent.
PPS obtained by the method described above may be in the form of a course or fine powder or in the form of fibres or platelets. It may be converted into another form before further processing if this appears to be advantageous~and it is moist (with solvent/water).
Polyphenylene sulphides obtained by no matter what method of preparation, e.g. ordinary commercial polyphenyl-ene sulphides~may also be freed from ash-forming residues by the process according to the invention after they have been suitably worked up. The moist polyarylene sulphides obtained, which have optionally been filtered or extracted, e.g. by pressure or suction filters, have a solids content of from 15 to 35%.
According to the invention, the polyarylene sulphides are subjected to a further mechanical demoisturising process which increases their solids content to 40-95~, preferably 50-95~. In the process according to the inven-tion, the proportion of ash-forming impurities does not only decrease in proportion to the quantity of liquid removed, as is normally the case when filters or centri-fuges are employed, but decreases to a much greater extent.
In the process according to the invention, the moist PPS with a solids content of 15 to 35% obtained after a preliminary filtration conventionally carried out in the known processes of preparation-is dosed continuously or discontinuously into suitable, known apparatus which are capable of applying a high pressure of from 5 to 400 bar ~e A 25 187 4 ~3~2~ ~ 1 on the product and at the same time subjecting it to shearing.
According to the invention, the apparatus used for this purpose may be, for example, pressure belts or high S pressure rollers. According to the particular apparatus employed, it is advantageous to take into account not only the pressure but also, for example, the linear pressure in the case of pressure belts, the absorption of force in the case of high pressure rollers, the velocity profiles in the-case of pressure rollers arranged in pairs and the surface characteristics of rollers or belts.
The shearing forces may be introduced by known measures, for example by rotating the rollers of a pair at different velocities or by squeezing the product between a pair of rollers which differ from one another in their surface characteristics.
Le A 25 187 13~
Examples Preparation of a polyphenylene sulphide by a known method (e.g. DE-OS 3 428 984).
1110 g of N-methylcaprolactam, 325.5 g of sodium sulphide hydrate (= 2.45 mol Na2S), 2.4 g of 50~ sodium hydroxide solution, 341.1 g of 1,4-dichlorobenzene (= 2.32 mol), 28.53 g of sodium acetate and 5.07 g of ~-amino-caproic acid (0.035 mol) are introduced under nitrogen into a 2 l three-necked flask equipped with a thermometer, a stirrer and a column with distillate divider. The reaction mixture is slowly heated to boiling. Water is separated from thelazeotropic mixture of water and p-dichlorobenzene distilling off and the p-dichlorobenzene is returned to the reaction vessel. No more water can be detected either in the distillate or in the sump after 2 hours.
Heating is continued under reflux for a further 9 hours.
The reaction mixture is then introduced into 1 l of isopropanol with vigorous stirring~The precipitated product is washed four t~s with four times its quantity of precipitating agent and then washed free from electrolyte with water to remove residues of inorganic salts (conductivity of wash water below 10 ~ S corresponding to a sodium chloride content of less than 5 ppm).
Le A 25 187 1~3~2d~ ~ ~
Example 1 Drying at elevated temperature in a vacuum as comparison example A polyarylene sulphide having a solids content of 18~ and obtained, for example, by the method described above, is dried in a drying cupboard under a vacuum of 10 mbar at 140C for 12 hours. The quantity of ash-forming impurities is then determined (see Table).
Example 2 Separation of PPS by centrifuging as comparison example A polyphenylene sulphide as described in Example 1 is introduced into a centrifuge and centrifuged for S minutes during which it is subjected to a pressure of ahout 20 bar. The results are shown in the Table Example 3 Drying on rollers as comparison example Example 2 is repeated but a pressure belt is used instead of the centrifuge. An increasing pressure finally reaching approximately 80 bar is applied to the product between three pairs of rollers while the two belts both move at the same velocity. The results are shown in the ~able. 0 Example 4 Drying on high pressure rollers as comparison example Example 2 is repeated but a pair of high pressure rollers is used instead of the centrifuges, and a pressure of about 200 bar is applied to the product. The surfaces of the rollers are smooth.
Examples according to the invention:
ExamPle 5 Example 3 is repeated with the velocities of the belts differing by 5~.
Example 6 Example 4 is repeated but the surfaces of the rollers are covered with 5 x 5 m- squares 2~m in depth t~ produce shearing.
The quantity of ash-forming impurities is determined by burning the product in a muffle furnace at 1 oooQc in the presence of atmospheric oxygen. The residue of this combustion is described as the ash-forming residue.
I~e A 25 1~7 7 Table Example Solids content Content in after mechanical ash forming dewateringimpurities based on PPS) 1 (Comparison) 18 0.75
Process for the purification of polyarylene sulphides This invention relates to a process for the purification of optionally branched polyarylene sulphides (PPS).
Polyarylene sulphides which have been purified according to the invention are distinguished by the reduced amount of ash-forming impurities contained in them.
Polyarylene sulphides and processes for their prepara-tion and isolation are known (e.g. US-P 4 071 509, JA-P 57 108-135, DE-OS 3 143 992, US-P 3 354 129, 3 457 242, 3 478 000, 3 687 907, 3 707 52~, 3 839 302, 3 941 664, 3 956 060, 4 046 749 and 4 178 435 and EP 79 144).
It is known, for example~that the solvent in which the polymerisation of the halogenated aromatic compounds and the source of sulphur was carried out may be evaporated from the reaction mixture and the inorganic salts may then be washed out of the remaining residue. Alternatively, the reaction mixture obtained after the polymerisation reaction may be immediately introduced into water without removal of the solvent and the precipitated residue may then be separated and washed. It is also known to wash the residue with organic solvents such as acetone, aromatic hydrocarbons, dimethylsulphoxide (DMSO) and N-methyl-pyrrolidone (NMP).
Polyarylene sulphides may also be purified by, for example, heating them in water with alkali metal acetates to temperatures just below their melting point (DE-OS
3 143 992), or by extraction with solvent mixtures s~ch as N-methylpyrrolidone and ethylene glycol (JA-P 57 108-135) or by heating them in organic amides in the presence of Le A 25 187 13~2~1~
certain alkali metal salts (US-P 4 071 509), etc.
The amount of ash-forming impurities in PPS 'may also be reduced by treatment of the aqueus PPS suspensions with atmospheric oxygen at temperatures above 200C but this may be accompanied by uncontrolled branching or cross-linking of the product (US-P 4 376 190).
Purified PPS has a lower concentration of ash-forming impurities and splits off a smaller amount of volatile compounds when processed and therefore causes less corrosion to the tools and apparatus used for its processes.
Furthermore, impurities left in PPS are liable to be troublesome when polyarylene sulphides are used for electric-al parts.
It has been found that the amount of ash-forming impurities contained in PPS can be considerably reduced if moist polyarylene sulphides obtained, for example, after they~have been washed to extract the soluble impur-ities in the process for their preparation~are demoisturised under a high pre~sure while subjected to shearing f~rces, e.g. in suitable pressure belts or between pressure rollers.
The present invention relates to a process for the purification of polyarylene sulphides with reduction of the quantity of ash-forming impurities, characterised in that moist polyarylene sulphides are demoisturised under a high pressure with concomitant application of shearing forces.
The process according to the invention may be used for treating, for example, straight chained or branched polyarylene sulphides which have been prepared by, for example, the known reaction of a~ 50 to 100 mol-% of dihalogenated aromatic compounds of the formula H
h - ~ (I), ~X ~
H H ~
Le A 25 187 2 ~
3L 3 ~
and 0 to 50 mol-% of dihalogenated aromatic compounds of the formula ~ R
X - ~ tII), wherein S X stands for halogens such as chlorine or bromine in the meta- or para-position to one another and R1 stands for identical or different groups and may denote hydrogen, alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl or two groups R1 in the ortho-position to one another may be linked together to form an aromatic or heterocyclic ring, and b) 0 to 5 mol-%, preferably 0.05 to 2.S mol-%, based on the sum of the dihalogenated aromatic compounds of formulae (I) and (II), of a tri- or tetra-halogenated aromatic compound of the formula ArXn (III) wherein Ar denotes an aromatic or heterocyclic group, X stands for a halogen such as chlorine or bromine and n stands for the number 3 or 4, and c) alkali metal sulphides, preferably sodium or potassium sulphide or mixtures thereof, preferably in the form of their hydrates or aqueous mixtures, optionally together with alkali metal hydroxides such as sodium or potassum hydroxide, the molar ratio of (a+b):c being in the range of from 0.85:1 to 1.15:1, preferably from 0.90:1 to 1.05:1, in d) organic solvents, preferably N-alkyl-lactams or peralkylated ureas, optionally with the addition of catalysts and/or cosolvents, using a molar ratio of alkali metal sulphides c) to organic solvents d) Le A 25 187 1312~ ~
in the range of from 1:2 to 1:15, and e) water in the form of water of hydration or free water, the molar ratio of c:d being in the range of from 1:0 to 1:6, at a reaction temperature of from 160GC
to 270C, optionally under excess pressure.
The reaction mixture obtained may be introduced into a precipitating agent after the polymerisation reaction.
The soluble impurities may be washed out of the precipitated polyarylene sulphide with water and/or some other extracting agent.
PPS obtained by the method described above may be in the form of a course or fine powder or in the form of fibres or platelets. It may be converted into another form before further processing if this appears to be advantageous~and it is moist (with solvent/water).
Polyphenylene sulphides obtained by no matter what method of preparation, e.g. ordinary commercial polyphenyl-ene sulphides~may also be freed from ash-forming residues by the process according to the invention after they have been suitably worked up. The moist polyarylene sulphides obtained, which have optionally been filtered or extracted, e.g. by pressure or suction filters, have a solids content of from 15 to 35%.
According to the invention, the polyarylene sulphides are subjected to a further mechanical demoisturising process which increases their solids content to 40-95~, preferably 50-95~. In the process according to the inven-tion, the proportion of ash-forming impurities does not only decrease in proportion to the quantity of liquid removed, as is normally the case when filters or centri-fuges are employed, but decreases to a much greater extent.
In the process according to the invention, the moist PPS with a solids content of 15 to 35% obtained after a preliminary filtration conventionally carried out in the known processes of preparation-is dosed continuously or discontinuously into suitable, known apparatus which are capable of applying a high pressure of from 5 to 400 bar ~e A 25 187 4 ~3~2~ ~ 1 on the product and at the same time subjecting it to shearing.
According to the invention, the apparatus used for this purpose may be, for example, pressure belts or high S pressure rollers. According to the particular apparatus employed, it is advantageous to take into account not only the pressure but also, for example, the linear pressure in the case of pressure belts, the absorption of force in the case of high pressure rollers, the velocity profiles in the-case of pressure rollers arranged in pairs and the surface characteristics of rollers or belts.
The shearing forces may be introduced by known measures, for example by rotating the rollers of a pair at different velocities or by squeezing the product between a pair of rollers which differ from one another in their surface characteristics.
Le A 25 187 13~
Examples Preparation of a polyphenylene sulphide by a known method (e.g. DE-OS 3 428 984).
1110 g of N-methylcaprolactam, 325.5 g of sodium sulphide hydrate (= 2.45 mol Na2S), 2.4 g of 50~ sodium hydroxide solution, 341.1 g of 1,4-dichlorobenzene (= 2.32 mol), 28.53 g of sodium acetate and 5.07 g of ~-amino-caproic acid (0.035 mol) are introduced under nitrogen into a 2 l three-necked flask equipped with a thermometer, a stirrer and a column with distillate divider. The reaction mixture is slowly heated to boiling. Water is separated from thelazeotropic mixture of water and p-dichlorobenzene distilling off and the p-dichlorobenzene is returned to the reaction vessel. No more water can be detected either in the distillate or in the sump after 2 hours.
Heating is continued under reflux for a further 9 hours.
The reaction mixture is then introduced into 1 l of isopropanol with vigorous stirring~The precipitated product is washed four t~s with four times its quantity of precipitating agent and then washed free from electrolyte with water to remove residues of inorganic salts (conductivity of wash water below 10 ~ S corresponding to a sodium chloride content of less than 5 ppm).
Le A 25 187 1~3~2d~ ~ ~
Example 1 Drying at elevated temperature in a vacuum as comparison example A polyarylene sulphide having a solids content of 18~ and obtained, for example, by the method described above, is dried in a drying cupboard under a vacuum of 10 mbar at 140C for 12 hours. The quantity of ash-forming impurities is then determined (see Table).
Example 2 Separation of PPS by centrifuging as comparison example A polyphenylene sulphide as described in Example 1 is introduced into a centrifuge and centrifuged for S minutes during which it is subjected to a pressure of ahout 20 bar. The results are shown in the Table Example 3 Drying on rollers as comparison example Example 2 is repeated but a pressure belt is used instead of the centrifuge. An increasing pressure finally reaching approximately 80 bar is applied to the product between three pairs of rollers while the two belts both move at the same velocity. The results are shown in the ~able. 0 Example 4 Drying on high pressure rollers as comparison example Example 2 is repeated but a pair of high pressure rollers is used instead of the centrifuges, and a pressure of about 200 bar is applied to the product. The surfaces of the rollers are smooth.
Examples according to the invention:
ExamPle 5 Example 3 is repeated with the velocities of the belts differing by 5~.
Example 6 Example 4 is repeated but the surfaces of the rollers are covered with 5 x 5 m- squares 2~m in depth t~ produce shearing.
The quantity of ash-forming impurities is determined by burning the product in a muffle furnace at 1 oooQc in the presence of atmospheric oxygen. The residue of this combustion is described as the ash-forming residue.
I~e A 25 1~7 7 Table Example Solids content Content in after mechanical ash forming dewateringimpurities based on PPS) 1 (Comparison) 18 0.75
2 (Comparison) 55 0.21
3 (Comparison) 63 0.16
4 (Comparison 90 0.11
5 according to the invention 65 0.03
6 according to the invention 90 0.01 Le A 25 187
Claims (9)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the purification of a polyarylene sulphide with reduction in the amount of ash-forming impurities contained therein, which process comprises demoisturizing a moist polyarylene sulphide under a high pressure with concomitant application of shearing force.
2. A process according to claim 1, wherein demoisturization is effected with pressure belts or high pressure rollers capable of applying the shearing force.
3. A process according to claim 1 wherein the polyarylene sulphide is obtained by polymerizing a halogenated aromatic compound in contact with a source of sulphur and a solvent.
4. A process according to claim 1 wherein the polyarylene sulphide is a polyphenylene sulphide.
S. A process according to claim 1 wherein the moist polyarylene sulphide has a solids content of 15 to 35%.
6. A process according to claim 1 wherein the moist polyarylene sulphide has a solids content of 50 to 95%.
7. A process according to any one of claims 1 to 6 wherein the polyarylene sulphide is passed between a pair of rollers rotating at different velocities to achieve said shearing force.
8. A process according to any one of claims 1 to 6 wherein the polyarylene sulphide is passed between a pair of rollers having different surface characteristics to achieve said shearing force.
9. A process according to any one of claims 1 to 6 wherein the polyarylene sulphide has been prepared by reacting a) 50 to 100 mol-% of a dihalogenated aromatic compound of the formula (I), and 0 to 50 mol-% of a dihalogenated aromatic compound of the formula (II) , wherein X stands for halogen and R1 stands for hydrogen, alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl or two groups R1 in the ortho position to one another may be linked together to form an aromatic or heterocyclic ring, and b) 0 to 5 mol-%, based on the sum of the dihalogenated aromatic compounds of formulae (I) and (II), of a tri-or tetra-halogenated aromatic compound of the formula ArXn (III) wherein Ar denotes an aromatic or heterocyclic group, X stands for halogen and n stands for the number 3 or 4, and c) an alkali metal sulphide, the molar ratio of (a+b):c being in the range of from 0.85:1 to 1.5:1, in d) an organic solvent, using a molar ratio of alkali metal sulphides c) to organic solvents d) in the range of from 1:2 to 1:15, and e) water in the form of water of hydration or free water, at a reaction temperature of from 160°C to 270°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19873713669 DE3713669A1 (en) | 1987-04-24 | 1987-04-24 | METHOD FOR PURIFYING POLYARYL SULFIDES |
| DEP3713669.0 | 1987-04-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1312411C true CA1312411C (en) | 1993-01-05 |
Family
ID=6326175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000564825A Expired - Fee Related CA1312411C (en) | 1987-04-24 | 1988-04-22 | Process for the purification of polyarylene sulphides |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0287948B1 (en) |
| JP (1) | JPS63280740A (en) |
| CA (1) | CA1312411C (en) |
| DE (2) | DE3713669A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5306803A (en) * | 1990-06-02 | 1994-04-26 | Bayer Aktiengesellschaft | Process for cleaning thermoplasts by friction compacting |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4071509A (en) * | 1976-08-13 | 1978-01-31 | Phillips Petroleum Company | Arylene sulfide polymer purification |
| US4373091A (en) * | 1980-11-07 | 1983-02-08 | Phillips Petroleum Company | Arylene sulfide polymer purification |
| JPS6153324A (en) * | 1984-08-23 | 1986-03-17 | Toyo Soda Mfg Co Ltd | Method of recovering solvent from polyalrylene sulfide reaction solution slurry |
| JPS6153325A (en) * | 1984-08-23 | 1986-03-17 | Toyo Soda Mfg Co Ltd | Method of recovering solvent from polyarylene sulfide reaction solution slurry and of purification through distillation |
| DE3433978A1 (en) * | 1984-09-15 | 1986-03-27 | Bayer Ag, 5090 Leverkusen | METHOD FOR ISOLATING POLYARYL SULFIDES |
| JPS61136523A (en) * | 1984-12-07 | 1986-06-24 | Toyo Soda Mfg Co Ltd | Production of polyarylene sulfide |
| DE3535455A1 (en) * | 1985-10-04 | 1987-04-09 | Bayer Ag | METHOD FOR ISOLATING POLYARYL SULFIDES |
-
1987
- 1987-04-24 DE DE19873713669 patent/DE3713669A1/en not_active Withdrawn
-
1988
- 1988-04-14 DE DE8888105931T patent/DE3871847D1/en not_active Expired - Lifetime
- 1988-04-14 EP EP88105931A patent/EP0287948B1/en not_active Expired - Lifetime
- 1988-04-18 JP JP63093612A patent/JPS63280740A/en active Pending
- 1988-04-22 CA CA000564825A patent/CA1312411C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0287948A3 (en) | 1988-12-21 |
| EP0287948B1 (en) | 1992-06-10 |
| DE3713669A1 (en) | 1988-11-17 |
| DE3871847D1 (en) | 1992-07-16 |
| EP0287948A2 (en) | 1988-10-26 |
| JPS63280740A (en) | 1988-11-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101470723B1 (en) | Process for production of polyarylene sulfides, and polyarylene sulfides | |
| JP5593580B2 (en) | Method for producing cyclic polyarylene sulfide mixture | |
| US5354841A (en) | Process for preparing poly(arylene sulfide) polymers using cyclic arylene sulfide oligomers | |
| EP0240016B1 (en) | Process for preparation of polyphenylene-sulfide resins | |
| KR101984418B1 (en) | Method for producing powdered polyarylene sulfide, and powdered polyarylene sulfide | |
| EP0279212A1 (en) | Recovering poly(arylene sulfide) oligomers from a poly(arylene sulfide) reaction mixture | |
| US3707528A (en) | Recovery of poly(arylene sulfide) reaction slurry constituents | |
| US5440009A (en) | Recovery of cyclic arylene sulfide oligomers | |
| EP0265524A1 (en) | Process for removing impurities from polyphenylene sulfide resin | |
| US3478000A (en) | Recovery of poly(arylene sulfides) | |
| JP2685337B2 (en) | Method for producing poly (arylene sulfide) composition | |
| JP6456742B2 (en) | Process for producing finely divided polyarylene sulfide and finely divided polyarylene sulfide | |
| CA1312411C (en) | Process for the purification of polyarylene sulphides | |
| US5247063A (en) | Process for the purification of polyarylene sulphides | |
| EP0271253B1 (en) | Process for recovering a polyarylene sulfide | |
| EP0594189A1 (en) | Production of poly(arylene sulfide)polymers containing reduced amounts of oligomers | |
| JP6366683B2 (en) | Heat-treated fine powder polyarylene sulfide, and production method for producing the heat-treated fine powder polyarylene sulfide | |
| EP0104560B1 (en) | Granular poly(arylene sulfide) recovery using evaporation | |
| JPH0657747B2 (en) | Method for purifying polyphenylene sulfide | |
| JP6733826B2 (en) | Method for producing polyarylene sulfide | |
| EP1189884A1 (en) | Removal of contaminants from n-methyl-2-pyrrolidone | |
| EP0594186A1 (en) | Production of granular poly(arylene sulfide) polymers containing reduced amounts of oligomers | |
| EP1226184B1 (en) | Methanol extraction of polar organic compounds and modifier compounds from poly(arylene sulfide) polymer and oligomer streams | |
| EP1242521A2 (en) | Recovery of modifier compounds and polar organic compounds from a poly(arylene sulfide) recycle mixture | |
| EP0594192A1 (en) | Production of poly(arylene sulfide)polymers containing reduced amounts of oligomers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKLA | Lapsed |