DE1016445B - Process for the production of cation-exchanging bead polymers with high grain strength - Google Patents
Process for the production of cation-exchanging bead polymers with high grain strengthInfo
- Publication number
- DE1016445B DE1016445B DEF12525A DEF0012525A DE1016445B DE 1016445 B DE1016445 B DE 1016445B DE F12525 A DEF12525 A DE F12525A DE F0012525 A DEF0012525 A DE F0012525A DE 1016445 B DE1016445 B DE 1016445B
- Authority
- DE
- Germany
- Prior art keywords
- bead polymers
- cation
- exchanging
- production
- bead
- 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
- 229920000642 polymer Polymers 0.000 title claims description 21
- 239000011324 bead Substances 0.000 title claims description 17
- 238000000034 method Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 11
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- VTPNYMSKBPZSTF-UHFFFAOYSA-N 1-ethenyl-2-ethylbenzene Chemical compound CCC1=CC=CC=C1C=C VTPNYMSKBPZSTF-UHFFFAOYSA-N 0.000 description 1
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- LBQJCDLKJGOHEA-UHFFFAOYSA-N 2-ethenylbut-3-enylbenzene Chemical compound C=CC(C=C)CC1=CC=CC=C1 LBQJCDLKJGOHEA-UHFFFAOYSA-N 0.000 description 1
- UXHQLGLGLZKHTC-CUNXSJBXSA-N 4-[(3s,3ar)-3-cyclopentyl-7-(4-hydroxypiperidine-1-carbonyl)-3,3a,4,5-tetrahydropyrazolo[3,4-f]quinolin-2-yl]-2-chlorobenzonitrile Chemical compound C1CC(O)CCN1C(=O)C1=CC=C(C=2[C@@H]([C@H](C3CCCC3)N(N=2)C=2C=C(Cl)C(C#N)=CC=2)CC2)C2=N1 UXHQLGLGLZKHTC-CUNXSJBXSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/26—Removing halogen atoms or halogen-containing groups from the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/38—Sulfohalogenation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
Verfahren zur Herstellung von kationenaustauschenden Perlpolymerisaten von hoher Kornfestigkeit Es ist aus der USA.-Patentschrift 2 366 007 bekanntgeworden, Perlpolymerisate mit kationenaustauschenden Eigenschaften herzustellen, indem man mit aromatischen Polyvinylverbindungen vernetzte Perlpolymerisate aus aromatischen Monovinylverbindungen mit sulfonierenden Mitteln behandelt. Die auf diese Weise erhaltenen sulfonierten, vernetzten Perlpolymerisate zeigen jedoch den Nachteil, daß sie beim Behandeln mit Wasser in Bruchstücke zerfallen und somit als Kationenaustauscher nur beschränkt einsatzfähig sind. Es sind nun auch bereits Verfahren zur Beseitigung dieses Nachteils vorgeschlagen worden. So soll z. B. nach der USA.-Patentschrift 2 466 675 der Kornzerfall der vorgenannten Sulfonierungsprodukte durch Eintragung in Elektrolytlösungen vermieden werden. Gemäß der USA.-Patentschrift 2 500 149 werden die vernetzten Perlpolymerisate vor der Sulfonierung in organischen Lösungsmitteln eingequollen. Die so vorbehandelten Polymerisate sollen nach der Sulfonierung gegen Wasser oder Elektrolytlösungen beständig sein. Durch diese besonderen Maßnahmen wird jedoch die Herstellung der vorgenannten Perlpolymerisate sehr erschwert.Process for the production of cation-exchanging bead polymers of high grain strength It is known from US Pat. No. 2,366,007 that Prepare bead polymers with cation-exchanging properties by Bead polymers crosslinked with aromatic polyvinyl compounds made from aromatic Monovinyl compounds treated with sulfonating agents. That way sulfonated, crosslinked bead polymers obtained, however, have the disadvantage that they disintegrate into fragments when treated with water and thus act as cation exchangers are only of limited use. There are already procedures for elimination this disadvantage has been suggested. So z. B. according to the USA patent 2,466,675 the grain disintegration of the aforementioned sulfonation products through registration be avoided in electrolyte solutions. According to U.S. Patent 2,500,149 the crosslinked bead polymers before sulfonation in organic solvents swollen. The polymers pretreated in this way are intended to counteract the sulfonation Resistant to water or electrolyte solutions. Through these special measures however, the production of the aforementioned bead polymers is made very difficult.
Es wurde nun gefunden, daß kationenaustauschende, vernetzte Perlpolymerisate von hoher Kornbeständigkeit in einfacher Weise erhalten werden können, indem Perlpolymerisate aus aromatischen Polyvinylverbindungen und/oder Perlmischpolymerisate dieser Verbindungen mit aromatischen Monovinylverbindungen durch Behandeln mit Chlorsulfonsäure in die Sulfochloride übergeführt und letztere zu den entsprechenden Sulfonsäuren hydrolysiert werden.It has now been found that cation-exchanging, crosslinked bead polymers of high grain resistance can be obtained in a simple manner by bead polymers from aromatic polyvinyl compounds and / or bead copolymers of these compounds with aromatic monovinyl compounds by treatment with chlorosulfonic acid in the Converted sulfochlorides and hydrolyzed the latter to the corresponding sulfonic acids will.
Die Sulfochloride der vorgenannten vernetzten Perlpolymerisate werden erhalten, indem die Behandlung mit Chlorsulfonsäure bei Temperaturen unterhalb 120° vorgenommen wird. Es war nicht vorauszusehen, daß unter diesen Bedingungen die Sulfochloride entstehen, da sich nach den bisher bekanntgewordenen Methoden bei der Einwirkung von Chlorsulfonsäure auf die genannten Polymerisate bei höheren Temperaturen ausschließlich oder in überwiegendem Maße die entsprechenden Sulfonsäuren bilden. Die Sulfochloride sind gegen Wasser bei Temperaturen bis zu 20° relativ beständig und werden beim Behandeln mit wärmerem Wasser in kurzer Zeit in die entsprechenden freien Sulfonsäuren übergeführt. Die auf diese Weise erhaltenen kationenaustauschenden Perlpolymerisate zeichnen sich gegenüber den durch direkte Sulfonierung von Perlpolymerisaten erhaltenen Austauschern durch eine besonders hohe mechanische Festigkeit aus.The sulfochlorides of the aforementioned crosslinked bead polymers are obtained by treating with chlorosulfonic acid at temperatures below 120 ° is made. It was not foreseeable that under these conditions the sulfochlorides arise because according to the previously known methods during the action of chlorosulfonic acid on the polymers mentioned at higher temperatures exclusively or predominantly form the corresponding sulfonic acids. The sulfochlorides are relatively resistant to water at temperatures of up to 20 ° and are used at Treat with warmer water in a short time into the corresponding free sulfonic acids convicted. The cation-exchanging bead polymers obtained in this way stand out over those obtained by direct sulfonation of bead polymers Exchangers are characterized by a particularly high mechanical strength.
Geeignete Polymerisate zur Durchführung des erfindungsgemäßen Verfahrens sind Perlpolymerisate von aromatischen Polyvinylverbindungen, wie z. B. Divinylbenzol, Divinyltoluol, Divinylnaphthalin, Divinyläthylbenzol, und die Mischpolymerisate dieser Verbindungen mit aromatischen Monovinylverbindungen, wie z. B. Styrol, Vinyltoluol, Vinylnaphthalin, Vinyläthylbenzol, Vinylxylol.Suitable polymers for carrying out the process according to the invention are bead polymers of aromatic polyvinyl compounds, such as. B. divinylbenzene, Divinyltoluene, divinylnaphthalene, divinylethylbenzene, and the copolymers these compounds with aromatic monovinyl compounds, such as. B. styrene, vinyl toluene, Vinyl naphthalene, vinyl ethylbenzene, vinyl xylene.
Von diesen Verbindungen haben sich insbesondere die Mischpolymerisate aus aromatischen Monovinylverbindungen und 1 bis 10 Gewichtsprozent aromatischen Polyvinylverbindungen für die Durchführung des vorliegenden Verfahrens als geeignet erwiesen.The copolymers in particular have proven themselves among these compounds from aromatic monovinyl compounds and 1 to 10 percent by weight aromatic Polyvinyl compounds to be suitable for carrying out the present process proven.
Beispiel 1 In 1000 ccm Chlorsulfonsäure werden bei 65 bis 70° in kleinen Anteilen innerhalb einer Stunde 500 ccm eines mit 10 Gewichtsprozent Divinylbenzol vernetzten Styrolpolymerisates (Korngröße 0,5 bis 1,00 mm) eingetragen und 10 Stunden bei dieser Temperatur nachbehandelt. Es wird dann ohne Wärmezufuhr weitere 6 Stunden gerührt, wobei die Temperatur des Ansatzes auf Zimmertemperatur fällt. Anschließend werden innerhalb von 3 Stunden 500 ccm ä0gewichtsprozentige Schwefelsäure zugesetzt und hierdurch die überschüssige Chlorsulfonsäure zersetzt. Dabei sinkt die Temperatur ohne äußere Kühlung von 22 auf 16°. Man kann nunmehr die Säurelösung durch Absaugen entfernen oder das Säure-Sulfochlorid-Gemisch auf 4000 g Eis geben. Anschließend wird das Polystyrolsulfochlorid sofort mit eiskaltem Wasser zur Entfernung der Schwefelsäure gewaschen und genutscht. Rohausbeute: 760 g.Example 1 In 1000 cc of chlorosulphonic acid at 65 to 70 ° in small Portions within one hour of 500 cc of one with 10 percent by weight divinylbenzene crosslinked styrene polymer (grain size 0.5 to 1.00 mm) entered and 10 hours post-treated at this temperature. It is then another 6 hours without the addition of heat stirred, the temperature of the batch falling to room temperature. Afterward 500 ccm of 0 weight percent sulfuric acid are added within 3 hours and thereby decomposes the excess chlorosulfonic acid. The temperature drops in the process without external cooling from 22 to 16 °. You can now remove the acid solution by suction remove or pour the acid-sulfochloride mixture onto 4000 g of ice. Afterward the polystyrene sulfochloride is immediately mixed with ice-cold water to remove the sulfuric acid washed and sucked. Raw yield: 760 g.
Das so erhaltene Polystyrolsulfochlorid wird durch Behandeln mit 50° warmem Wasser zersetzt und die hierbei frei werdende Salzsäure sowie der Schwefelgehalt der entstandenen Sulfosäure bestimmt. Es werden folgende Werte erhalten: Einsatz: 500 ccm Styrolpolymerisat, entsprechend 325 g; gewonnen: 400 g trockene Polystyrolsulfosäure; Gesamtschwefel = 66,2 g Schwefel; Gesamtchlor = 70 g Chlor = 95,2%, berechnet auf den obigen Gesamtschwefelwert.The polystyrene sulfochloride obtained in this way is treated with 50 ° decomposed in warm water and the hydrochloric acid released as well as the sulfur content the resulting sulfonic acid is determined. The following values are obtained: Mission: 500 ccm of styrene polymer, corresponding to 325 g; recovered: 400 g dry polystyrene sulfonic acid; Total sulfur = 66.2 grams of sulfur; Total chlorine = 70 g chlorine = 95.2%, calculated on the above total sulfur value.
Beispie12 Zu 1000 ccm Chlorsulfonsäure werden 500 ccm mit 10 Gewichtsprozent Divinylbenzol vernetztes Styrolpolymerisat der Kornfraktion 0,5 bis 1,00 mm unter langsamem Rühren bei Zimmertemperatur auf einmal zugesetzt. Es tritt keine Temperatursteigerung ein. Es wird 72 Stunden lang bei Zimmertemperatur gerührt; das Reaktionsgemisch ist dann ein dicker Brei. Nach etwa 72 Stunden wird für etwa 3 Stunden ein Temperaturanstieg bis auf J- 35° beobachtet, dann fällt die Temperatur wieder auf 20°. Nach weiteren 12 Stunden (insgesamt 87 Stunden) wird in einem Zeitraum von 3 Stunden 500 ccm Schwefelsäure (80gewichtsprozentig) zugesetzt, der Überschuß an Chlorsulfonsäuren zersetzt und die Chlorsulfonierung beendet. Nach dem Überführen der Sulfochloridgruppe in die Sulfosäuregruppe durch Wasserbehandlung erhält man eine Polystyrolsulfosäure mit einem Schwefelgehalt von 14,9% Schwefel (berechnet auf trockene, freie Sulfosäure), ohne daß hierbei ein Kornzerfall des Harzes eintritt.Example12 To 1000 cc of chlorosulfonic acid, 500 cc with 10 percent by weight Divinylbenzene crosslinked styrene polymer of the grain fraction 0.5 to 1.00 mm below added all at once to slow stirring at room temperature. There is no increase in temperature a. It is stirred for 72 hours at room temperature; the reaction mixture is then a thick mush. After about 72 hours there will be a temperature rise for about 3 hours observed down to J- 35 °, then the temperature falls back to 20 °. After further For 12 hours (a total of 87 hours), 500 cc of sulfuric acid is used over a period of 3 hours (80 percent by weight) added, the excess of chlorosulfonic acids decomposed and the chlorosulfonation ended. After converting the sulfochloride group into the A polystyrene sulfonic acid is obtained with sulfonic acid group by treatment with water a sulfur content of 14.9% sulfur (calculated on dry, free sulfonic acid), without causing the resin to break down.
Bcispie13 Ein nach dem Beispiel 1 dargestelltes und isoliertes Polystyrolsulfochlorid wird mit 50° warmem Wasser (14° dH) in einem Beaufschlagungsverhältnis 1 :6/ Stunde über 24 Stunden behandelt. Das Volumen des Polystyrolsulfochlorids beträgt vor der Behandlung 1000 ccm und erreicht bereits nach 3 Stunden den Maximalwert von 1450 ccm, den es auch noch nach 24 Stunden ohne jeden Kornzerfall am Ende der Wasserbehandlung aufweist. Zu diesem Zeitpunkt ist das Sulfochlorid in die Sulfosäure übergeführt, die nunmehr eine Spaltung der im Wasser gelösten Salze vornimmt und sich mit den Kationen der Härtebildner belädt. Die Gesamtaustauschkapazität beträgt zu diesem Zeitpunkt noch 5.76 g Ca 0 je 100 ccm feuchter Austauscher. Es wird mit Kochsalzlösung regeneriert und nach dem Auswaschen ein im Korn völlig intakter und neutral reagierender Na-Austauscher gewonnen. Das Volumen ist auf 1100 ccm geschrumpft.Bcispie13 A polystyrene sulfochloride prepared and isolated according to Example 1 is with 50 ° warm water (14 ° dH) in a loading ratio of 1: 6 / hour Treated over 24 hours. The volume of the polystyrene sulfochloride is before Treatment 1000 ccm and already reaches the maximum value of 1450 after 3 hours ccm, which it is still after 24 hours without any grain disintegration at the end of the water treatment having. At this point the sulfochloride is converted into the sulfonic acid, which now splits the salts dissolved in the water and deals with the Cations of the hardeners are loaded. The total exchange capacity is to this At this point, 5.76 g Ca 0 per 100 ccm moist exchanger. It is made with saline regenerated and after washing out a completely intact and neutral reacting grain in the grain Na exchanger obtained. The volume has shrunk to 1100 ccm.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF12525A DE1016445B (en) | 1953-08-04 | 1953-08-04 | Process for the production of cation-exchanging bead polymers with high grain strength |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF12525A DE1016445B (en) | 1953-08-04 | 1953-08-04 | Process for the production of cation-exchanging bead polymers with high grain strength |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1016445B true DE1016445B (en) | 1957-09-26 |
Family
ID=7087030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF12525A Pending DE1016445B (en) | 1953-08-04 | 1953-08-04 | Process for the production of cation-exchanging bead polymers with high grain strength |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1016445B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3122456A (en) * | 1959-02-16 | 1964-02-25 | Bayer Ag | Purfication of sugar solutions by means of spongy ion exchangers |
| US11667085B1 (en) | 2007-06-04 | 2023-06-06 | Encore Wire Corporation | Method and apparatus for applying labels to cable |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2366007A (en) * | 1942-08-11 | 1944-12-26 | Gen Electric | Production of synthetic polymeric compositions comprising sulphonated polymerizates of poly-vinyl aryl compounds and treatment of liquid media therewith |
| US2466675A (en) * | 1945-04-02 | 1949-04-12 | Dow Chemical Co | Production of sulfonated resin ion exchange agents in stable granular form |
| US2500149A (en) * | 1947-02-21 | 1950-03-14 | Dow Chemical Co | Sulfonation of copolymers of monovinyl-and polyvinyl-aromatic compounds |
| FR960585A (en) * | 1942-08-11 | 1950-04-20 | ||
| US2638445A (en) * | 1945-05-05 | 1953-05-12 | Standard Oil Dev Co | Sulfonated high molecular weight styrene-olefin copolymers |
-
1953
- 1953-08-04 DE DEF12525A patent/DE1016445B/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2366007A (en) * | 1942-08-11 | 1944-12-26 | Gen Electric | Production of synthetic polymeric compositions comprising sulphonated polymerizates of poly-vinyl aryl compounds and treatment of liquid media therewith |
| FR960585A (en) * | 1942-08-11 | 1950-04-20 | ||
| US2466675A (en) * | 1945-04-02 | 1949-04-12 | Dow Chemical Co | Production of sulfonated resin ion exchange agents in stable granular form |
| US2638445A (en) * | 1945-05-05 | 1953-05-12 | Standard Oil Dev Co | Sulfonated high molecular weight styrene-olefin copolymers |
| US2500149A (en) * | 1947-02-21 | 1950-03-14 | Dow Chemical Co | Sulfonation of copolymers of monovinyl-and polyvinyl-aromatic compounds |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3122456A (en) * | 1959-02-16 | 1964-02-25 | Bayer Ag | Purfication of sugar solutions by means of spongy ion exchangers |
| US11667085B1 (en) | 2007-06-04 | 2023-06-06 | Encore Wire Corporation | Method and apparatus for applying labels to cable |
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