DE1001669B - Process for the production of selectively cation-permeable exchange membranes - Google Patents
Process for the production of selectively cation-permeable exchange membranesInfo
- Publication number
- DE1001669B DE1001669B DEP10093A DEP0010093A DE1001669B DE 1001669 B DE1001669 B DE 1001669B DE P10093 A DEP10093 A DE P10093A DE P0010093 A DEP0010093 A DE P0010093A DE 1001669 B DE1001669 B DE 1001669B
- Authority
- DE
- Germany
- Prior art keywords
- exchange membranes
- production
- chlorosulfonic acid
- cation
- cation exchange
- 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
- 238000000034 method Methods 0.000 title claims description 8
- 239000012528 membrane Substances 0.000 title description 20
- 238000004519 manufacturing process Methods 0.000 title description 5
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 claims description 15
- 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 14
- 238000006277 sulfonation reaction Methods 0.000 claims description 3
- 244000286663 Ficus elastica Species 0.000 claims 1
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 229920001195 polyisoprene Polymers 0.000 claims 1
- 238000005341 cation exchange Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- -1 aliphatic vinyl hydrocarbons Chemical class 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000011088 parchment paper Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2231—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds
- C08J5/2243—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions involving unsaturated carbon-to-carbon bonds obtained by introduction of active groups capable of ion-exchange into compounds of the type C08J5/2231
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
Verfahren zur Herstellung von selektiv Kationen durchlässigen Austaus chmembranen Gegenstand der Erfindung ist ein Verfahren zur Herstellung von selektiv Kationen durchlässigen Austauschmembranen, im folgenden kurz Kationenaustauschmembranen genannt, durch Sulfonierung von Folien aliphatischer Vinylpolymerisate, wobei die Sulfonierung unter solchen Bedingungen durchgeführt wird, daß Kationenaustauschmembranen hoher mechanischer Festigkeit entstehen, die für technische Zwecke, z. B. der Elektrodialyse, geeignet sind. Process for the preparation of selectively cation-permeable exchanges chmembranen The invention is a process for the production of selective Cation-permeable exchange membranes, in the following briefly cation exchange membranes called, by sulfonation of films of aliphatic vinyl polymers, the Sulphonation is carried out under such conditions that cation exchange membranes high mechanical strength that is necessary for technical purposes, e.g. B. electrodialysis, are suitable.
Es ist bekannt, daß aliphatische Vinylpolymerisate, wie z. B. synthetische Kautschuke und sauerstoffhaltige aliphatische Vinylpolymerisate, durch Einwirkung von Sulfonierungs.mitteln bei höheren Temperaturen in Kationenaustauscher übergeführt werden können. Versucht man, diese bekannten Verfahren auf Folien anzuwenden, um iu Kationenaustauschmemhranen zu gelangen, so führt solches nicht zum Ziel, da dabei die Folienstruktur völlig zerstort wird und nulr feinkörnige Materialien geringer mechanischer Festigkeit entstehen. It is known that aliphatic vinyl polymers such. B. synthetic Rubbers and oxygen-containing aliphatic vinyl polymers, by action converted by sulfonating agents into cation exchangers at higher temperatures can be. If one tries to apply these known methods to foils in order to To get to cation exchange membranes, this does not lead to the goal, because it does so the film structure is completely destroyed and only fine-grained materials are reduced mechanical strength arise.
Es wurde nun gefunden, daß die Herstellung von Kationenaustauscbmemhranen hoher mechanischer Festigkeit dadurch gelingt, daß Folien aliphaüscher Vinylpolymerisate der Einwirkung von Sulfonierungsmitteln bei Temperaturen unterhalb 600, vorzugsweise unterhalb 300, unterworfen werden. It has now been found that the production of cation exchange memhranes high mechanical strength is achieved by the fact that foils are made of aliphatic vinyl polymers the action of sulfonating agents at temperatures below 600, preferably below 300.
Das erfindungsgemäße Verfahren ist mit besonderem Vorteil auf Folien von Polymerisaten aliphatischer Vi.nylkohlenwasserstoffe und aliphatischer Vinylhalogenkohlenwasserstoffe anwendbar. The method according to the invention is particularly advantageous on foils of polymers of aliphatic vinyl hydrocarbons and aliphatic vinyl halogenated hydrocarbons applicable.
Als Sulfonierungsmittel kommen insbesondere konzentrierte oder verdünnte Chlorsulfonsäure, Gemische von Chlorsulfonsäure und Sulfurylchilorid sowie Lösungen von S 03 O, in anorganischen oder organischen Verdünnungsmitteln in Betracht. Particularly concentrated or diluted sulfonating agents are used Chlorosulfonic acid, mixtures of chlorosulfonic acid and sulfuryl chloride and solutions of S 03 O, in inorganic or organic diluents.
Beispiel 1 Eine Polyvinylchloridfolie von 0,2 mm Stärke wird bei 200 in Chlorsulfonsäure getaucht, wobei die Folie unter Quellung allmählich eine dunkle Farbe annimmt. Example 1 A polyvinyl chloride film 0.2 mm thick is used in 200 dipped in chlorosulfonic acid, the film gradually swelling a becomes dark in color.
Nach 20 Stunden wird die Folie aus der Chlorsulfonsäure genommen und zur Entfernung der anhaftenden Chlorsulfonsäure zunächst mit 960/obiger Schwefelsäure, dann mit Wasser und anschließend mit 50/oiger Natronlauge gewaschen. Nach Auswaschen der Natronlauge wird eine Kationenlaustau.schmembran in der Na-Form erhalten, die etwa 150/0 größer ist, als die eingesetzte Polyvinylchloridfolie. Die Membran kann getrocknet und anschließend wieder mit Wasser befeuchtet werden, ohne daß sie zerspringt.After 20 hours, the film is removed from the chlorosulfonic acid and to remove the adhering chlorosulphonic acid first with 960 / above sulfuric acid, then washed with water and then with 50% sodium hydroxide solution. After washing out the sodium hydroxide solution is a Kationenlaustau.schmembran obtained in the Na form, the is about 150/0 larger than the polyvinyl chloride film used. The membrane can dried and then re-moistened with water without cracking.
Des weiteren zeigt die Membran hohe Zerreiß- und Knickfestigkeit. Die Austauschkapazität der Membran beträgt etwa 1,2 Millival/g.Furthermore, the membrane shows high tensile strength and kink resistance. The exchange capacity of the membrane is about 1.2 millivalents / g.
Beispiel 2 Eine Polyäthylenfolie von 0,1 mm Stärke wird bei 150 in Chlorsuifonsäure getaucht, wobei sie im Verlauf einiger Stunden eine dunkle Farbe annimmt. Nach 5 Stunden wird die Folie aus der Chlorsulfonsäure genommen und die überschüssige Chlorsulfonsäure wird durch Waschen mit Äthylenchlorid entfernt. Das anhaftende Äthylenchlorid läßt man verdunsten und die Membran wird nach Einweichen in 20/oiger NaOh mit Wasser gewaschen. Die erhaltene Kationenaustauschmembran besitzt eine Stärke von 0,12 mm, eine Austauschkapazität von 1,5 Millivallg und die mechanische Festigkeit von Pergamentpapier. Example 2 A 0.1 mm thick polyethylene sheet is used at 150 in Chlorosulfonic acid is immersed, turning a dark color over the course of a few hours accepts. After 5 hours, the film is removed from the chlorosulfonic acid and the Excess chlorosulfonic acid is removed by washing with ethylene chloride. That adhering ethylene chloride is allowed to evaporate and the membrane is after soaking washed in 20% NaOH with water. The cation exchange membrane obtained has a thickness of 0.12 mm, an exchange capacity of 1.5 millivallg and the mechanical Strength of parchment paper.
Will man das Arbeiten mit reiner Chlorsulfonsäure vermeiden, so kann auch in Gegenwart von Verdünnungsmitteln, wie z. B. Athylenchlorid gearbeitet werden, doch sind hierbei zur Erzielung von Kationenaustauscbmembranen der gleichen Kapazität längere Einwirkungszeiten erforderlich. If you want to avoid working with pure chlorosulfonic acid, you can even in the presence of diluents, such as. B. ethylene chloride are worked, but they are of the same capacity to achieve cation exchange membranes longer exposure times required.
Beispiel 3 Eine Polyäthylenfolie von 0,15 mm Stärke wurde in eine 200/obige Lösung von Chlorsulfonsäure in Äthylenchlorid getaucht. Die Umsetzung verläuft, wie man aus dem Verlauf der Verfärbung ersehen kann, viel langsamer als bei Einwirkung von reiner Chlorsuifonsäure. Nach 20 Stunden wird die jetzt dunkle Folie aus der Lösung genommen, mit Äthylenchlorid gewaschen und dann weiter, wie in Beispiel 2 beschrieben, behandelt. Example 3 A polyethylene film 0.15 mm thick was in a 200 / above solution of chlorosulfonic acid immersed in ethylene chloride. The implementation runs, as can be seen from the course of the discoloration, much slower than when exposed to pure chlorosulfonic acid. After 20 hours it will now be dark Slide taken out of the solution, washed with ethylene chloride and then continue like described in Example 2, treated.
Die erhaltene Kationenaustauschmembran besitzt eine Stärke von 0,19 mm, eine Austauschkapazität von 1,6 Millival/g und eine hohe mechanische Festigkeit. The cation exchange membrane obtained has a thickness of 0.19 mm, an exchange capacity of 1.6 millivalents / g and a high mechanical Strength.
Als besonders vorteilhaft hat sich ferner erwiesen, die Chlorsulfonierung mit einem Gemisch von Chiorsulfonsäure und Sulfurylchlorid durchzuführen, da hierbei Membranen noch höherer Festigkeit erhalten werden.Chlorosulfonation has also proven to be particularly advantageous to be carried out with a mixture of chlorosulfonic acid and sulfuryl chloride, since this is the case Even higher strength membranes can be obtained.
Beispiel 4 Eine Polyäthylenfolie von 0,06 mm Stärke wurde in ein Gemisch von 40 Teilen Chlorsulfonsäure und 60 Teilen Sulfurylchlorid bei 200 getaucht. Nach achtstündiger Einwirkungszeit wurde die Folie aus der Lösung entfernt und nach Waschen mit Äfflylen chlorid, wie in Beispiel 2 beschrieben, weiterbehandelt. Example 4 A polyethylene film 0.06 mm thick was in a Mixture of 40 parts of chlorosulfonic acid and 60 parts of sulfuryl chloride immersed at 200. After an eight hour exposure time, the film was removed from the solution and after Washing with Äfflylene chloride, as described in Example 2, treated further.
Die erhaltene 0,09 mm starke Kationenaustaaschmembran besaß eine Kapazität von 1,5 Millivallg und eine hohe Zerreiß- und Biegefestigkeit.The obtained 0.09 mm thick cation exchange membrane had a capacity of 1.5 millivallg and a high tensile strength and flexural strength.
An Stelle der bisher verwendeten Chlorsulfonsäure kann auch SOs gelöst in z. B. Äthylenchlorid oder rauchende Schwefelsäure, z. B. 600/oiges Oleum verwendet werden. In place of the chlorosulfonic acid previously used, SOs can also be dissolved in z. B. ethylene chloride or fuming sulfuric acid, e.g. B. 600% oleum used will.
Beispiel 5 Eine Polyvinylchloridfolie von 0,5 mm Stärke wurde mit 600/oigem Oleum übergossen und bei 250 10 Stunden stehen gelassen. Nach Auswaschen des überschüssigen Oleums zunächst mit 960/oiger Schwefelsäure und dann mit Wasser wurde eine Kationenaustauschmembran guter mechanischer Festigkeit mit einer Kapazität von 1,1 Millivallg erhalten. Example 5 A polyvinyl chloride film 0.5 mm thick was made with 600% oleum poured over it and left to stand at 250 for 10 hours. After washing out of the excess oleum first with 960% sulfuric acid and then with water became a cation exchange membrane of good mechanical strength with capacity of 1.1 millivallg obtained.
Wurde die Behandlung bei 1100 durchgeführt, so fand eine heftige Reaktion statt, die zu einer völligen Zerstörung der Folienstruktur führte. überraschend an dem erfindungsgemäßen Verfahren zur Herstellung von Kationenaustauschmembranen ist insbesondere, daB 1. unter den erfindungsgemäß vorgesehenen milden Temperaturbedingungen eine Sulfonierung der rein aliphatischen Polymerisate in größerem Umfange eintritt, 2. die erhaltenen Suifonierungsprodukte selbst in verdünnten Alkalien unlöslich sind, also als Kationenaustauscher verwendbar sind, 3. die erhaltenen Kationenaustauschmembranen hohe mechanische Festigkeit besitzen und so für technische Zwecke verwendbar sind, 4. die erhaltenen Kationenaustauschmembranen unempfindlich gegen Austrocknen und Wiederbefeuchten sind. When the treatment was carried out at 1100, a violent one took place Reaction instead, which led to a complete destruction of the film structure. surprised on the process according to the invention for the production of cation exchange membranes is in particular that 1. under the mild temperature conditions provided according to the invention sulfonation of the purely aliphatic polymers occurs to a large extent, 2. The suifonation products obtained are insoluble even in dilute alkalis are, so can be used as cation exchangers, 3. the cation exchange membranes obtained have high mechanical strength and can thus be used for technical purposes, 4. The cation exchange membranes obtained are insensitive to drying out and Rewet are.
Durch sogenannte Chlorsnlfonierung bzw. Sulfochlorierung, d. h. durch Einwirkung von 502 und Cl2 auf Polyäthylen gelingt es nicht, Kationenaustauschmembranen herzustellen, da hierbei nur lösliche Produkte erhalten werden. By so-called chlorine solubilization or sulfochlorination, i. H. by The effects of 502 and Cl2 on polyethylene fail to create cation exchange membranes to produce, since only soluble products are obtained here.
PATENTANSPCHE: 1. Verfahren zur Herstellung von selektiv Kationen durchlässigen Austauschmembranen, dadurch gekennzeichnet, daß Folien aus Polymerisaten einfach ungesättigter aliphatischer Verbinzungen in an sich bekannter Weise bei Temperaturen unterhalb 600, insbesondere unterhalb 300, sulfoniert werden. PATENT CLAIM: 1. Method for the production of selective cations permeable exchange membranes, characterized in that films made from polymers monounsaturated aliphatic compounds in a manner known per se Temperatures below 600, in particular below 300, are sulfonated.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP10093A DE1001669B (en) | 1953-07-11 | 1953-07-11 | Process for the production of selectively cation-permeable exchange membranes |
| GB2033454A GB747948A (en) | 1953-07-11 | 1954-07-12 | Improvements in the production of cation-exchange membranes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP10093A DE1001669B (en) | 1953-07-11 | 1953-07-11 | Process for the production of selectively cation-permeable exchange membranes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1001669B true DE1001669B (en) | 1957-01-31 |
Family
ID=7362675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEP10093A Pending DE1001669B (en) | 1953-07-11 | 1953-07-11 | Process for the production of selectively cation-permeable exchange membranes |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1001669B (en) |
| GB (1) | GB747948A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1154623B (en) | 1958-04-09 | 1963-09-19 | American Mach & Foundry | Process for the production of selective membranes |
| DE1177611B (en) | 1954-07-24 | 1964-09-10 | Asahi Garasu Kabushiki Kaisha | Cation-permeable membranes |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1135656B (en) * | 1957-01-03 | 1962-08-30 | Nat Res Dev | Process for the production of cation-permeable membranes |
| GB981562A (en) * | 1960-12-01 | 1965-01-27 | The Negev Institute | Method of producing ion-exchange material and permselective membranes from polyolefines and the products produced thereby |
| US3320218A (en) * | 1963-04-05 | 1967-05-16 | Dow Chemical Co | Cross-linked sulfonated aliphatic hydrocarbon polymers |
| NL7812340A (en) * | 1977-12-28 | 1979-07-02 | Sumitomo Chemical Co | SEMIPERMEABEL MEMBRANE AND METHOD FOR MANUFACTURING IT. |
| JPS5657836A (en) * | 1979-10-16 | 1981-05-20 | Asahi Chem Ind Co Ltd | Porous hydrophilic polyolefin resin membrane and its preparation |
| WO2007044353A2 (en) * | 2005-10-04 | 2007-04-19 | Ballard Power Systems Inc. | Methods for making sulfonated non-aromatic polymer electrolyte membranes |
| CN115477713A (en) * | 2021-05-31 | 2022-12-16 | 中国石油化工股份有限公司 | A kind of sulfonic acid resin catalyst and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2212786A (en) * | 1939-05-01 | 1940-08-27 | Du Pont | Production of sulphonyl chlorides of olefin polymers |
| US2333142A (en) * | 1940-09-18 | 1943-11-02 | Infilco Inc | Water softening process |
| US2525247A (en) * | 1946-03-05 | 1950-10-10 | American Cyanamid Co | Cation exchange resins |
| DE763926C (en) * | 1934-04-14 | 1951-01-29 | Permutit Ag | Manufacture of carbon cation exchangers |
| US2586363A (en) * | 1947-05-19 | 1952-02-19 | Du Pont | Vulcanizable chlorosulfonated polymers |
| US2597438A (en) * | 1951-05-12 | 1952-05-20 | Rohm & Haas | Cation-exchange polymers of the sulfonic type |
-
1953
- 1953-07-11 DE DEP10093A patent/DE1001669B/en active Pending
-
1954
- 1954-07-12 GB GB2033454A patent/GB747948A/en not_active Expired
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE763926C (en) * | 1934-04-14 | 1951-01-29 | Permutit Ag | Manufacture of carbon cation exchangers |
| US2212786A (en) * | 1939-05-01 | 1940-08-27 | Du Pont | Production of sulphonyl chlorides of olefin polymers |
| US2333142A (en) * | 1940-09-18 | 1943-11-02 | Infilco Inc | Water softening process |
| US2525247A (en) * | 1946-03-05 | 1950-10-10 | American Cyanamid Co | Cation exchange resins |
| US2586363A (en) * | 1947-05-19 | 1952-02-19 | Du Pont | Vulcanizable chlorosulfonated polymers |
| US2597438A (en) * | 1951-05-12 | 1952-05-20 | Rohm & Haas | Cation-exchange polymers of the sulfonic type |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1177611B (en) | 1954-07-24 | 1964-09-10 | Asahi Garasu Kabushiki Kaisha | Cation-permeable membranes |
| DE1154623B (en) | 1958-04-09 | 1963-09-19 | American Mach & Foundry | Process for the production of selective membranes |
Also Published As
| Publication number | Publication date |
|---|---|
| GB747948A (en) | 1956-04-18 |
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